Methacrylate and acrylate polymers and processes for making same

ABSTRACT

Polar polymers having the following formula: 
     
       
         FG-(Q) d -R n -Z-J-[A(R 1 R 2 R 3 )] x    (I)  
       
     
     wherein FG is H or a protected or non-protected functional group; Q is a polar hydrocarbyl group derived by incorporation of a polar compound selected from group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof; d is an integer from 10 to 2000; R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; J is oxygen, sulfur, or nitrogen; [A(R 1 R 2 R 3 )] x  is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of Elements; R 1 , R 2 , and R 3  are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, and living anionic polymerization processes for preparing the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.08/677,793, filed Jul. 10, 1996, now U.S. Pat. No. 5,900,464, issued May4, 1999, which is related to commonly owned U.S. Provisional ApplicationSerial No. 60/006,062, filed Jul. 25, 1995, and claims the benefit ofits earlier date under 35 USC Section 119(e).

FIELD OF THE INVENTION

This invention relates to novel functionalized polar polymers andprocesses for producing the same. More particularly, the inventionrelates novel functionalized methacrylate and acrylate polymers andprocesses for the anionic polymerization of the same.

BACKGROUND OF THE INVENTION

Living polymerizations can provide advantages over other polymerizationtechniques, such as well-defined polymer structures and low degree ofcompositional heterogeneity. Many of the variables that affect polymerproperties can be controlled, including molecular weight, molecularweight distribution, copolymer composition and microstructure,stereochemistry, branching and chain end functionality.

Living anionic polymerization of styrene and diene monomers were firstdescribed by Szwarc and his coworkers. See M. Szwarc, Nature 178, 1169(1956) and M. Szwarc, et al., J. Am. Chem. Soc. 78, 2656 (1956). Whileliving anionic polymerization can be effective for the controlledpolymerization of non-polar monomers, anionic polymerization of polarmonomers, such as methacrylates and acrylates, is more problematic. Thepresence of a carbonyl group in acrylate monomers complicates anionicpolymerization of polar monomers. For example, nucleophilic attack atthe carbonyl group can lead to no initiation or polymerizationtermination.

Various techniques have been proposed to address the problem of anionicpolymerization of methacrylate and acrylate monomers. Proposals includelow polymerization temperatures (−78° C.), the use of stericallyhindered initiators, bulky alkyl ester groups, and the addition ofcomplexing agents, such as crown ethers, lithium chloride and lithiumalkoxides. Other techniques include metal-free anionic polymerizationusing delocalized carbanion initiators with nonmetallictetrabutylammonium salts (see, e.g., M. T. Reetz, Angew. Chem. Int. Ed.Eng. 27, 994 (1988)); group transfer polymerization, using asilicon-based initiator (O. W. Webster, et al., European Patent 0 068887 (1986)); and immortal polymerization using aluminum porphyrins asinitiators (M. Kuroki et al., J. Am. Chem. Soc. 109, 4739 (1987); Y.Hosokawa, et al., Macromolecules 24, 824 (1991)). See also, T. P Davis,et al., Rev. Macromol. Chem. Phys., C34(2), 243-324 (1994) and H. Hsiehand R. Quirk, Anionic Polymerization (Marcel Dekker, Inc., New York1996) for a more complete review.

Although useful, these and other techniques of anionic polymerization ofmethacrylate and acrylate monomers can suffer from drawbacks, such asineffectiveness at higher temperatures, slow reaction rates, broadmolecular weight distributions, poor copolymerization with polar andnon-polar comonomers, and the like. Further, these processes can beexpensive, thus limiting their commercial applicability. These problemscan be compounded when polymerizing acrylate monomers, which are morereactive than methacrylate monomers.

SUMMARY OF THE INVENTION

The present invention provides novel polar polymers, includingfunctionalized, telechelic, heterotelechelic, and multi-branched or starmethacrylate and acrylate polymers, and processes for preparing thesame. The novel polymers have applications in a variety of areas,including use in low VOC coatings, adhesives, and as viscosity index(V.I.) improvers for lubricants.

The present invention also provides processes for anionic polymerizationof polar monomers to produce the polymers of the invention. Thesepolymers are prepared from protected functionalized initiators which arereacted with an appropriate diaryl alkenyl group, such as1,1-diphenylethylene, to provide a stabilized carbanion. A polarmonomer, preferably methyl methacrylate, is polymerized in the presenceof the initiator to provide a living anion.

The resultant living anion can be quenched, for example with acidicmethanol, to afford a protected, mono-functional polar polymer, andremoval of the protecting group results in a functionalized polarpolymer.

Alternatively, the resultant living anion can be quenched with variousfunctionalizing agents, such as ethylene oxide, carbon dioxide,epichlorohydrin, and the like, to afford a mono-protected telechelicpolar polymer. The functional groups on the termini of the polymer canbe the same (such as two hydroxyl groups) or different (such as onehydroxyl group and one amino group).

Protected, functionalized polar star polymers can also prepared bylinking the living anion with suitable linking agents, such as ethyleneglycol dimethylacrylate, glycerol trimethacrylate,α,α′-dibromo-p-xylene, α,α′,α″-tribromo-mesitylene, and the like.Subsequent deprotection affords functionalized polar stars.

In contrast to star polymers of the prior art, the moleculararchitecture of compounds of the present invention can be preciselycontrolled. For example, each arm of the multi-arm polymer can contain afunctional group (protected or non-protected), and the functional groups(and/or protecting groups) can be the same or different. The starpolymers can also include both functional and non-functional ends. Thenature of the functional group, and/or protecting group, and/ornon-functional group can be varied simply by changing the initiator, andthe ratio of one functional group to another functional group, or of onefunctional group to a non-functional group, can be adjusted by simplyvarying the ratio of initiators to one another. Further, monomeridentity, monomer composition and molecular weight of both functionaland non-functional arms can be independently manipulated by varying themonomer charged by each initiator. Still further, the number of polymerarms can be adjusted by varying the nature of the coupling agent, andthe ratio of living polymer to the coupling agent.

DETAILED DESCRIPTION OF THE INVENTION

The polar polymers of the present invention have the following formula:

FG-(Q)_(d)-R_(n)-Z-J-[A(R¹R²R³)]_(x)   (I)

or

L[(Q)_(d)R_(n)-Z-J-[A(R¹R²R³)]_(x)]_(m)   (II)

wherein FG is H or a protected or non-protected functional group; Q is ahydrocarbyl group derived by incorporation of a polar monomer selectedfrom group consisting of esters, amides, and nitrites of acrylic andmethacrylic acid, and mixtures thereof with one another and/or withother polar monomers; d is an integer from 10 to 2000; R is a saturatedor unsaturated hydrocarbyl group derived by incorporation of a compoundselected from the group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is oxygen, sulfur, or nitrogen;[A(R¹R²R³)]_(x) is a protecting group, in which A is an element selectedfrom Group IVa of the Periodic Table of Elements; R¹, R², and R³ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, aryl or substituted aryl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbonatoms; and x is dependent on the valence of J and varies from one when Jis oxygen or sulfur to two when J is nitrogen. L in formula II is alinking agent selected from the group consisting of reactive halogencompounds and multifunctional acrylates, as described below.

Removal of the protecting group (deprotection) produces polymers withoxygen, sulfur or nitrogen functional groups on the ends of thepolymers. The residual aliphatic unsaturation can be optionally removedby hydrogenation before or after removal of the protecting groups. Thesefunctional groups can then participate in various copolymerizationreactions by reaction of the functional groups on the ends of thepolymer with selected difunctional or polyfunctional comonomers and/orlinking or coupling agents, as described in more detail below.

The polar monomer to be anionically polymerized is chosen from the groupof organic compounds that can be polymerized anionically (i.e. in areaction initiated by an organo-alkali metal), and preferably isselected from group consisting of esters, amides, and nitrites ofacrylic and methacrylic acid, and mixtures thereof. The polar monomersmay be polymerized singly, as a mixture thereof with one another and/orother polar monomers, to form random or tapered copolymers, orsequentially with one another and/or other polar monomers to form blockcopolymers.

Exemplary polar monomers include, without limitation, methylmethacrylate, methyl acrylate, t-butyl methacrylate, t-butyl acrylate,ethyl methacrylate, N,N-dimethylacrylamide, lauryl methacrylate, stearylmethacrylate, 2,3-epoxypropyl methacrylate, decyl methacrylate, andoctyl methacrylate. For reference, see Macromolecules, 14, 1599 (1981);Polymer 31, 106 (1990); Polymer, 34, 2875 (1993).

The process of the invention generally comprises initiatingpolymerization of a polar monomer as described above in a polar,hydrocarbon, or mixed hydrocarbon-polar solvent medium, preferably at atemperature of −80° C. to 20° C., with a protected functionalorganolithium initiator to form an intermediate mono-protectedmono-functional living anion. Preferably, the initiator is reacted withan appropriate diaryl alkenyl group, such as 1,1-diphenylethylene, toprovide a stabilized carbanion prior to polymerization. The protectedfunctional organolithium initiators can be reacted with polar monomerseither singly, sequentially, or as mixtures thereof with one another orwith other polar comonomers.

The mono-protected mono-functional living anion can be quenched orterminated by addition of a suitable proton donor, such as methanol,isopropanol, acetic acid, and the like, to provide a mono-functionalpolar polymer. Alternatively, polymerization can be followed byfunctionalization of the resultant living anion with a suitableelectrophile to provide a mono-protected, di-functional polymer. Thedi-functional polymer may be telechelic, i.e., contain two functionalgroups, which are the same, per molecule at the termini of the polymer.The polymer can also be heterotelechelic, having differentfunctionalities at opposite ends of the polymer chain. This isrepresented schematically by the formula A-------B, wherein A and B aredifferent functional groups.

Electrophiles that are useful in functionalizing the polymeric livinganion include, but are not limited to, alkylene oxides, such as ethyleneoxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur;carbon dioxide; halogens such as chlorine, bromine and iodine;alkenylhalosilanes, omega-alkenylarylhalosilanes, andhaloalkyltrialkoxysilanes, such as chlorotrimethylsilane andstyrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propanesultone; amides, including cyclic amides, such as caprolactam,N-benzylidene trimethylsilylamide, and dimethyl formamide; siliconacetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allylbromide and allyl chloride; methacryloyl chloride; amines, includingprimary, secondary, tertiary and cyclic amines, such as3-(dimethylamino)-propyl chloride andN-(benzylidene)trimethylsilylamine; epihalohydrins, such asepichlorohydrin, epibromohydrin, and epiiodohydrin, and other materialsas known in the art to be useful for terminating or end cappingpolymers. These and other useful functionalizing agents are described,for example, in U.S. Pat. Nos. 3,786,116 and 4,409,357, the entiredisclosure of each of which is incorporated herein by reference. Thepolymer is optionally hydrogenated, either before or after removal ofthe protecting group, or before or after functionalization.

Exemplary organolithium initiators useful in the present inventioninclude initiators selected from the group consisting ofomega-(tert-alkoxy)-1-alkyllithiums, omega-(tert-alkoxy)-1-alkyllithiumschain extended with conjugated alkadienes, alkenylsubstituted aromatichydrocarbons, and mixtures thereof,omega-(tert-alkylthio)-1-alkyllithiums,omega-(tert-alkylthio)-1-alkyllithiums chain extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums chain-extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, and omega-(bis-tert-alkylsilylamino)-1-alkyllithiums.

Initiators useful in the preparation of polymers of the presentinvention are also represented by the following formula:

M-R_(n)-Z-J-[A(R¹R²R³)]_(x)   (III)

wherein M is an alkali metal; R is a saturated or unsaturatedhydrocarbyl group derived by incorporation of a compound selected fromthe group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is a hetero atom, e.g., oxygen, sulfur, ornitrogen; A is an element selected from Group IVa of the Periodic Tableof Elements; R¹, R², and R³ are each independently selected fromhydrogen, alkyl, substituted alkyl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, and cycloalkyl and substituted cycloalkyl containing 5 to 12carbon atoms; and x is dependent on the valence of J and varies from onewhen J is oxygen or sulfur to two when J is nitrogen.

These initiators (III) can be prepared by reaction of protectedorganolithium compounds of the following formula:

M-Z-J-[A(R¹R²R³)]_(x)   (IV)

wherein each of M, Z, J, A, R¹, R², R³, and x are the same as definedabove, with one or more conjugated alkadienes (such as butadiene orisoprene), alkenylsubstituted aromatic hydrocarbons (such as styrene oralpha-methylstyrene), and mixtures thereof, to form an extendedhydrocarbon chain between M and Z in Formula (IV), which extended chainis denoted as R_(n) in Formula (III). As noted above, the initiator isadducted to an appropriate diphenyl alkenyl group, such as1,1-diphenylethylene, to provide a stabilized carbanion prior topolymerization.

The compounds of Formula (IV) can be prepared by reacting in an inertsolvent a selected tertiary amino-1-haloalkane,omega-hydroxy-protected-1-haloalkane, oromega-thio-protected-1-haloalkane, depending on whether J is to be N, Oor S, (the alkyl portions of the haloalkyl groups contain 3 to 25 carbonatoms) with an alkali metal, preferably lithium, at a temperaturebetween about 35° C. and about 130° C., preferably at the solvent refluxtemperature, to form a protected monofunctional alkali metal initiator(of Formula IV), which is then optionally reacted with a one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromatichydrocarbons, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic hydrocarbons, in a predominantly alkane,cycloalkane, or aromatic reaction solvent, which solvent contains 5 to10 carbon atoms, and mixtures of such solvents to produce amonofunctional initiator with an extended chain or tether between themetal atom (M) and element (J) in Formula (III) above and mixturesthereof with compounds of Formula (IV). R in Formula (III) is preferablyderived from conjugated 1,3-dienes. While A in the protecting group[A(R¹R²R³)] of the formulae above can be any of the elements in GroupIVa of the Periodic Table of the Elements, carbon and silicon currentlyappear the most useful, especially when polymerizing conjugated dienes.

Incorporation of R groups into the M-Z linkage to form the compounds ofFormula (III) above involves addition of compounds of the Formula

M-Z-J-[A(R¹R²R³)]_(x)

where the symbols have the meanings ascribed above, across the carbon tocarbon double bonds in compounds selected from the consisting of one ormore conjugated diene hydrocarbons, one or more alkenylsubstitutedaromatic hydrocarbons, or mixtures of one or more dienes with one ormore alkenylsubstituted aromatic hydrocarbons, to produce newcarbon-lithium bonds of an allylic or benzylic nature, much like thosefound in a propagating polyalkadiene or polyarylethylene polymer chainderived by anionic initiation of the polymerization of conjugated dienesor arylethylenes. These new carbon-lithium bonds are now activatedtoward polymerization and so are much more efficient in promotingpolymerization than the precursor M-Z (M=Li) bonds themselves.

Tertiary amino-1-haloalkanes useful in practicing this invention arecompounds of the following general structures:

X-Z-N[A(R¹R²R³)]₂

and

wherein X is halogen, preferably chlorine or bromine; Z is a branched orstraight chain hydrocarbon tether or connecting group which contains3-25 carbon atoms, which tether may also contain aryl or substitutedaryl groups; A is an element selected from Group IVa of the PeriodicTable of the Elements; R¹, R², and R³ are independently defined ashydrogen, alkyl, substituted alkyl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, or cycloalkyl and substituted cycloalkyl groups containing 5 to12 carbon atoms; and m is an integer from 1 to 7, and their employmentas initiators in the anionic polymerization of olefin containingmonomers in an inert, hydrocarbon solvent optionally containing a Lewisbase. The process reacts selected tertiary amino-1-haloalkanes whosealkyl groups contain 3 to 25 carbon atoms, with lithium metal at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

Anionic polymerizations employing the tertiary amine initiators areconducted in an inert solvent, preferably a non-polar solvent,optionally containing an ethereal modifier, using an olefinic monomerwhich is an alkenylsubstituted aromatic hydrocarbon or a 1,3-diene at atemperature of about −30° C. to about 150° C. The polymerizationreaction proceeds from initiation to propagation and is finallyterminated with appropriate reagents so that the polymer ismono-functionally or di-functionally terminated. The polymers may have amolecular weight range of about 1000 to 10,000 but the molecular weightcan be higher. Typically 5 to 50 milli-moles of initiator is used permole of monomer.

Tertiary amino-1-haloalkanes useful in the practice of this inventioninclude, but are not limited to, 3-(N,N-dimethylamino)-1-propyl halide,3-(N,N-dimethylamino)-2-methyl-1-propyl halide,3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-dimethylamino)-1-butyl halide, 5-(N,N-dimethylamino)-1-pentylhalide, 6-(N,N-dimethylamino)-1-hexyl halide,3-(N,N-diethylamino)-1-propyl halide,3-(N,N-diethylamino)-2-methyl-1-propyl halide,3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentylhalide, 6-(N,N-diethylamino)-1-hexyl halide,3-(N-ethyl-N-methylamino)-1-propyl halide,3-(N-ethyl-N-methylamino)-2-methyl-1-propyl halide,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide,4-(N-ethyl-N-methylamino)-1-butyl halide,5-(N-ethyl-N-methylamino)-1-pentyl halide,6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propylhalide, 3-(piperidino)-2-methyl-1-propyl halide,3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butylhalide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl halide,3-(pyrrolidino)-1-propyl halide, 3-(pyrrolidino)-2-methyl-1-propylhalide, 3-(pyrrolidino)-2,2-dimethyl-1-propyl halide,4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide,6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl halide,3-(hexamethyleneimino)-2-methyl-1-propyl halide,3-(hexamethyleneimino)-2,2-dimethyl-1-propyl halide,4-(hexamethyleneimino)-1-butyl halide, 5-(hexamethyleneimino)-1-pentylhalide, 6-(hexamethyleneimino)-1-hexyl halide,3-(N-isopropyl-N-methyl)-1-propyl halide,2-(N-isopropyl-N-methyl)-2-methyl-1-propyl halide,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide group ispreferably selected from chlorine and bromine.

Omega-hydroxy-protected-1-haloalkanes useful in producing monofunctionalether initiators useful in practicing this invention have the followinggeneral structure:

X-Z-O—[C(R¹R²R³)]

wherein X is halogen, preferably chlorine or bromine; Z is a branched orstraight chain hydrocarbon group which contains 3-25 carbon atoms,optionally containing aryl or substituted aryl groups; and R¹, R², andR³ are independently defined as hydrogen, alkyl, substituted alkylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, aryl or substituted aryl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, or cycloalkyl and substitutedcycloalkyl groups containing 5 to 12 carbon atoms, and their employmentas initiators in the anionic polymerization of olefin containingmonomers in an inert, hydrocarbon solvent optionally containing a Lewisbase. The process reacts selected omega-hydroxy-protected-1-haloalkaneswhose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

Anionic polymerizations employing the monofunctional ether initiatorsare conducted in an inert solvent, preferably a non-polar solvent,optionally containing an ethereal modifier, using an olefinic monomerwhich is an alkenylsubstituted aromatic hydrocarbon or a 1,3-diene at atemperature of about −30° C. to about 150° C. The polymerizationreaction proceeds from initiation to propagation and is finallyterminated with appropriate reagents so that the polymer ismono-functionally or di-functionally terminated. The polymers may have amolecular weight range of about 1000 to 10,000 but the molecular weightcan be higher. Typically 5 to 50 milli-moles of initiator is used permole of monomer.

The precursor omega-protected-1-haloalkanes (halides) can be preparedfrom the corresponding haloalcohol by standard literature methods. Forexample, 3-(1,1-dimethylethoxy)-1-chloropropane can be synthesized bythe reaction of 3-chloro-1-propanol with 2-methylpropene according tothe method of A. Alexakis, M. Gardette, and S. Colin, TetrahedronLetters, 29, 1988, 2951. The method of B. Figadere, X. Franck and A.Cave, Tetrahedron Letters, 34, 1993, 5893, which involves the reactionof the appropriate alcohol with 2-methyl-2-butene catalyzed by borontrifluoride etherate, can be employed for the preparation of the t-amylethers. The alkoxy, alkylthio or dialkylamino substituted ethers, forexample 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, can besynthesized by reaction of the corresponding substituted alcohol, forinstance 3-methylthio-1-propanol, with analpha-bromo-omega-chloroalkane, for instance 1-bromo-6-hexane, accordingto the method of J. Almena, F. Foubelo and M. Yus, Tetrahedron, 51,1995, 11883. The compound 4-(methoxy)-1-chlorobutane, and the higheranalogs, can be synthesized by the ring opening reaction oftetrahydrofuran with thionyl chloride and methanol, according to theprocedure of T. Ferrari and P. Vogel, SYNLETT, 1991, 233. Thetriphenylmethyl protected compounds, for example3-(triphenylmethoxy)-1-chloropropane, can be prepared by the reaction ofthe haloalcohol with triphenylmethylchloride, according to the method ofS. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.

Omega-hydroxy-protected-1-haloalkanes prepared in accordance with thisearlier process useful in practicing this invention include, but are notlimited to, 3-(1,1-dimethylethoxy)-1-propyl halide,3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylethoxy)-1-butyl halide, 5-(1,1-dimethylethoxy)-1-pentylhalide, 6-(1,1-dimethylethoxy)-1-hexyl halide,8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1-propylhalide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylpropoxy)-1-butyl halide, 5-(1,1-dimethylpropoxy)-1-pentylhalide, 6-(1,1-dimethylpropoxy)-1-hexyl halide,8-(1,1-dimethylpropoxy)-1-octyl halide, 4-(methoxy)-1-butyl halide,4-(ethoxy)-1-butyl halide, 4-(propyloxy)-1-butyl halide,4-(1-methylethoxy)-1-butyl halide,3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide,4-(triphenylmethoxy)-1-butyl halide,3-[3-(dimethylamino)-1-propyloxy]-1-propyl halide,3-[2-(dimethylamino)-1-ethoxy]-1-propyl halide,3-[2-(diethylamino)-1-ethoxy]-1-propyl halide,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyl halide,3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl halide,4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide,6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide,3-[2-(methoxy)-1-ethoxy]-1-propyl halide,3-[2-(ethoxy)-1-ethoxy]-1-propyl halide,4-[2-(methoxy)-1-ethoxy]-1-butyl halide,5-[2-(ethoxy)-1-ethoxy]-1-pentyl halide,3-[3-(methylthio)-1-propyloxy]-1-propyl halide,3-[4-(methylthio)-1-butyloxy]-1-propyl halide,3-(methylthiomethoxy)-1-propyl halide,6-[3-(methylthio)-1-propyloxy]-1-hexyl halide,3-[4-(methoxy)-benzyloxy]-1-propyl halide,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyl halide,3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide,8-[4-(methoxy)-benzyloxy]-1-octyl halide,4-[4-(methylthio)-benzyloxy]-1-butyl halide,3-[4-(dimethylamino)-benzyloxy]-1-propyl halide,6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide,5-(triphenylmethoxy)-1-pentyl halide, 6-(triphenylmethoxy)-1-hexylhalide, and 8-(triphenylmethoxy)-1-octyl halide. The halo- or halidegroup is preferably selected from chlorine and bromine.

U.S. Pat. No. 5,362,699 discloses a process for the preparation ofhydrocarbon solutions of monofunctional ether initiators derived fromomega-hydroxy-silyl-protected-1-haloalkanes of the following generalstructure:

X-Z-O—[Si(R¹R²R³)]

wherein X is halogen, preferably chlorine or bromine; Z is a branched orstraight chain hydrocarbon group which contains 3-25 carbon atoms,optionally containing aryl or substituted aryl groups; and R¹, R², andR³ are independently defined as saturated and unsaturated aliphatic andaromatic radicals, and their employment as initiators in the anionicpolymerization of olefin containing monomers in an inert, hydrocarbonsolvent optionally containing a Lewis base. The process reacts selectedomega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25carbon atoms, with lithium metal at a temperature between about 25° C.and about 40° C., in an alkane or cycloalkane reaction solventcontaining 5 to 10 carbon atoms and mixtures of such solvents.

Anionic polymerizations employing the monofunctional siloxy etherinitiators are conducted in an inert solvent, preferably a non-polarsolvent, optionally containing an ethereal modifier, using an olefinicmonomer which is an alkenylsubstituted aromatic hydrocarbon or a1,3-diene at a temperature of about −30° C. to about 150° C. Thepolymerization reaction proceeds from initiation to propagation and isfinally terminated with appropriate reagents so that the polymer ismono-functionally or di-functionally terminated. The polymers may have amolecular weight range of about 1000 to 10,000 but the molecular weightcan be higher. Typically 5 to 50 milli-moles of initiator is used permole of monomer.

Omega-silyl-protected-1-haloalkanes prepared in accordance with thisearlier process useful in practicing this invention include, but are notlimited to, 3-(t-butyldimethylsilyloxy)-1-propyl halide,3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide,4-(t-butyldimethylsilyloxy)-1-butyl halide,5-(t-butyldimethyl-silyloxy)-1-pentyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide,8-(t-butyldimethylsilyloxy)-1-octyl halide, 3-(t-butyldiphenylylsilyloxy)-1-propyl halide, 3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide, 4-(t-butyldiphenylylsilyloxy)-1-butyl halide,6-(t-butyldiphenylsilyloxy)-1-hexyl halide and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or halidegroup is preferably selected from chlorine and bromine.

Monofunctional thioether initiators useful in the practice of thisinvention are derived from omega-thio-protected-1-haloalkanes of thefollowing general structure:

X-Z-S-[A(R¹R²R³)]

wherein X is halogen, preferably chlorine or bromine; Z is a branched orstraight chain hydrocarbon group which contains 3-25 carbon atoms,optionally containing aryl or substituted aryl groups; [A(R¹R²R³)] is aprotecting group in which A is an element selected from Group IVa of thePeriodic Table of the Elements, and R¹, R², and R³ are independentlydefined as hydrogen, alkyl, substituted alkyl groups containing loweralkyl, lower alkylthio, and lower dialkylamino groups, aryl orsubstituted aryl groups containing lower alkyl, lower alkylthio, andlower dialkylamino groups, or cycloalkyl and substituted cycloalkylgroups containing 5 to 12 carbon atoms, and their employment asinitiators in the anionic polymerization of olefin containing monomersin an inert, hydrocarbon solvent optionally containing a Lewis base. Theprocess reacts selected omega-thioprotected-1-haloalkyls whose alkylgroups contain 3 to 25 carbon atoms, with lithium metal at a temperaturebetween about 35° C. and about 130° C., preferably at the refluxtemperature of an alkane, cycloalkane or aromatic reaction solventcontaining 5 to 10 carbon atoms and mixtures of such solvents.

Anionic polymerizations employing the monofunctional thioetherinitiators are conducted in an inert solvent, preferably a non-polarsolvent, optionally containing an ethereal modifier, using an olefinicmonomer which is an alkenylsubstituted aromatic hydrocarbon or a1,3-diene at a temperature of about −30° C. to about 150° C. Thepolymerization reaction proceeds from initiation to propagation and isfinally terminated with appropriate reagents so that the polymer ismono-functionally or di-functionally terminated. The polymers may have amolecular weight range of about 1000 to 10,000 but the molecular weightcan be higher. Typically 5 to 50 milli-moles of initiator is used permole of monomer.

The initiator precursor, omega-thio-protected-1-haloalkanes (halides),can be prepared from the corresponding halothiol by standard literaturemethods. For example, 3-(1,1-dimethylethylthio)-1-propylchloride can besynthesized by the reaction of 3-chloro-1-propanthiol with2-methylpropene according to the method of A. Alexakis, M. Gardette, andS. Colin, Tetrahedron Letters, 29, 1988, 2951. Alternatively, reactionof 1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a baseaffords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of B.Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893,which involves the reaction of the appropriate thiol with2-methyl-2-butene catalyzed by boron trifluoride etherate, can beemployed for the preparation of the t-amyl ethers. Additionally,5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by themethod of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995,11883. This synthesis involves the reaction of the appropriate thiolwith an alkyllithium, then reaction of the lithium salt with thecorresponding alpha, omega dihalide. 3-(Methylthio)-1-propylchloride canbe prepared by chlorination of the corresponding alcohol with thionylchloride, as taught by D. F. Taber and Y. Wang, J. Org, Chem., 58, 1993,6470. Methoxymethylthio compounds, such as6-(methoxymethylthio)-1-hexylchloride, can be prepared by the reactionof the omega-chloro-thiol with bromochloromethane, methanol, andpotassium hydroxide, by the method of F. D. Toste and I. W. J. Still,Synlett, 1995, 159. T-Butyldimethylsilyl protected compounds, forexample 4-(t-butyldimethylsilylthio)-1-butylhalide, can be prepared fromt-butyldimethylchlorosilane, and the corresponding thiol, according tothe method described in U.S. Pat. No. 5,493,044.

Omega-thio-protected 1-haloalkanes prepared in accordance with thisearlier process useful in practicing this invention include, but are notlimited to, 3-(methylthio)-1-propylhalide,3-(methylthio)-2-methyl-1-propylhalide,3-(methylthio)-2,2-dimethyl-1-propylhalide,4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide,6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide,3-(methoxymethylthio)-1-propylhalide,3-(methoxymethylthio)-2-methyl-1-propylhalide,3-(methoxymethylthio)-2,2-dimethyl-1-propylhalide,4-(methoxymethylthio)-1-butylhalide,5-(methoxymethylthio)-1-pentylhalide,6-(methoxymethylthio)-1-hexylhalide,8-(methoxymethylthio)-1-octylhalide,3-(1,1-dimethylethylthio)-1-propylhalide,3-(1,1-dimethylethylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylethylthio)-1-butylhalide,5-(1,1-dimethylethylthio)-1-pentylhalide,6-(1,1-dimethylethylthio)-1-hexylhalide,8-(1,1-dimethylethylthio)-1-octylhalide,3-(1,1-dimethylpropylthio)-1-propylhalide,3-(1,1-dimethylpropylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylpropylthio)-1-butylhalide,5-(1,1-dimethylpropylthio)-1-pentylhalide,6-(1,1-dimethylpropylthio)-1-hexylhalide,8-(1,1-dimethylpropylthio)-1-octylhalide,3-(cyclopentylthio)-1-propylhalide,3-(cyclopentylthio)-2-methyl-1-propylhalide,3-(cyclopentylthio)-2,2-dimethyl-1-propylhalide,4-(cyclopentylthio)-1-butylhalide, 5-(cyclopentylthio)-1-pentylhalide,6-(cyclopentylthio)-1-hexylhalide, 8-(cyclopentylthio)-1-octylhalide,3-(cyclohexylthio)-1-propylhalide,3-(cyclohexylthio)-2-methyl-1-propylhalide,3-(cyclohexylthio)-2,2-dimethyl-1-propylhalide,4-(cyclohexylthio)-1-butylhalide, 5-(cyclohexylthio)-1-pentylhalide,6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide,3-(t-butyldimethylsilylthio)-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,4-(t-butyldimethylsilylthio)-1-butylhalide,6-(t-butyldimethylsilylthio)-1-hexylhalide and3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or halidegroup is preferably selected from chlorine and bromine.

Examples of functionalized organolithium initiators (III) include, butare not limited to, tert-alkoxy-alkyllithiums such as3-(1,1-dimethylethoxy)-1-propyllithium and its more hydrocarbon-solubleisoprene chain-extended oligomeric analog (n=2),3-(tert-butyldimethylsilyloxy)-1-propyllithium (n=0),tert-alkylthio-alkyllithiums such as3-(1,1-dimethylethylthio)-1-propyllithium and its morehydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2),3-(dimethylamino)-1-propyllithium and its more hydrocarbon-solubleisoprene chain-extended oligomeric analog (n=2) and3-(di-tert-butyldimethylsilylamino)-1-propyllithium, and mixturesthereof. Further examples of protected functionalized initiators thatmay be employed in this invention include, but are not limited to,3-(1,1-dimethylethoxy)-1-propyllithium,3-(1,1-dimethylethoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethoxy)-1-butyllithium,5-(1,1-dimethylethoxy)-1-pentyllithium,6-(1,1-dimethylethoxy)-1-hexyllithium,8-(1,1-dimethylethoxy)-1-octyllithium,3-(1,1-dimethylpropoxy)-1-propyllithium,3-(1,1-dimethylpropoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropoxy)-1-butyllithium,5-(1,1-dimethylpropoxy)-1-pentyllithium,6-(1,1-dimethylpropoxy)-1-hexyllithium,8-(1,1-dimethylpropoxy)-1-octyllithium,3-(t-butyldimethylsilyloxy)-1-propyllithium,3-(t-butyldimethylsilyloxy)-2-methyl-1-propyllithium,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilyloxy)-1-butyllithium,5-(t-butyldimethylsilyloxy)-1-pentyllithium,6-(t-butyldimethylsilyloxy)-1-hexyllithium,8-(t-butyldimethylsilyloxy)-1-octyllithium and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyllithium,3-(dimethylamino)-1-propyllithium,3-(dimethylamino)-2-methyl-1-propyllithium,3-(dimethylamino)-2,2-dimethyl-1-propyllithium,4-(dimethylamino)-1-butyllithium, 5-(dimethylamino)-1-pentyllithium,6-(dimethylamino)-1-hexyllithium, 8-(dimethylamino)-1-propyllithium,4-(ethoxy)-1-butyllithium, 4-(propyloxy)-1-butyllithium,4-(1-methylethoxy)-1-butyllithium,3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,4-(triphenylmethoxy)-1-butyllithium,3-[3-(dimethylamino)-1-propyloxy]-1-propyllithium,3-[2-(dimethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyllithium,3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,4-[3-(dimethylamino)-1-propyloxy]-1-butyllithium,6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,3-[2-(methoxy)-1-ethoxy]-1-propyllithium,3-[2-(ethoxy)-1-ethoxy]-1-propyllithium,4-[2-(methoxy)-1-ethoxy]-1-butyllithium,5-[2-(ethoxy)-1-ethoxy]-1-pentyllithium,3-[3-(methylthio)-1-propyloxy]-1-propyllithium,3-[4-(methylthio)-1-butyloxy]-1-propyllithium,3-(methylthiomethoxy)-1-propyllithium,6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,3-[4-(methoxy)-benzyloxy]-1-propyllithium,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyllithium,3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,8-[4-(methoxy)-benzyloxy]-1-octyllithium,4-[4-(methylthio)-benzyloxy]-1-butyllithium,3-[4-(dimethylamino)-benzyloxy]-1-propyllithium,6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,5-(triphenylmethoxy)-1-pentyllithium,6-(triphenylmethoxy)-1-hexyllithium, and8-(triphenylmethoxy)-1-octyllithium,3-(hexamethyleneimino)-1-propyllithium,4-(hexamethyleneimino)-1-butyllithium,5-(hexamethyleneimino)-1-pentyllithium,6-(hexamethyleneimino)-1-hexyllithium,8-(hexamethyleneimino)-1-octyllithium,3-(t-butyldimethylsilylthio)-1-propyllithium,3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilylthio)-1-butyllithium,6-(t-butyldimethylsilylthio)-1-hexyllithium,3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,3-(1,1-dimethylethylthio)-1-propyllithium,3-(1,1-dimethylethylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethylthio)-1-butyllithium,5-(1,1-dimethylethylthio)-1-pentyllithium,6-(1,1-dimethylethylthio)-1-hexyllithium,8-(1,1-dimethylethylthio)-1-octyllithium,3-(1,1-dimethylpropylthio)-1-propyllithium,3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropylthio)-1-butyllithium,5-(1,1-dimethylpropylthio)-1-pentyllithium,6-(1,1-dimethylpropylthio)-1-hexyllithium, and8-(1,1-dimethylpropylthio)-1-octyllithium and their more hydrocarbonsoluble conjugated alkadiene, alkenylsubstituted aromatic hydrocarbon,and mixtures thereof, chain extended oligomeric analogs (n=1-5).

Functionalized polymers of Formula (I) can be further reacted with othercomonomers such as di or polyesters, di- or polyiisocyanates, di-,poly-, or cyclic amides, di- and polycarboxylic acids, and di- andpolyols in the presence of a strong acid catalyst to simultaneouslydeprotect the functional polymer and polymerize both functional endsthereof to produce novel segmented block polymers. Alternatively, thefunctional polymer of Formula (I) can be reacted with other comonomersin the absence of a strong acid catalyst to yield block copolymers,while maintaining the integrity of the protective group to provide afunctional block copolymer. Still another alternative is to remove theprotective group of the functional polymer of Formula (I) and topolymerize a functional block copolymer of the preceding sentence withthe same or other comonomers to produce novel segmented block polymers.

The polymerization solvent is preferably a polar solvent, although ahydrocarbon, or mixtures of polar and hydrocarbon solvents can be used.Examples of polar solvents include, but are not limited to, diethylether, dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyltert-butyl ether, diazabicyclo[2.2.2]octane, triethylamine,tributylamine, N,N,N′,N′-tetramethylethylene diamine (TMEDA), and1,2-dimethoxyethane (glyme).

Inert hydrocarbon solvents useful in practicing this invention include,but are not limited to, inert liquid alkanes, cycloalkanes and aromaticsolvents such as alkanes and cycloalkanes containing five to ten carbonatoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane,methylcycloheptane, octane, decane and the like, and aromatic solventscontaining six to ten carbon atoms such as toluene, ethylbenzene,p-xylene, m-xylene, o-xylene, n-propylbenzene, isopropylbenzene,n-butylbenzene, and the like. The amount of the inert solvent addeddepends on factors such as the nature of the monomer, the temperature ofthe polymerization, and the identity of the inert solvent.

As noted above, if desired, the protecting groups can be removed fromthe polymer. This deprotection can be performed either prior to or afterthe optional hydrogenation of the residual aliphatic unsaturation. Forexample, to remove tert-alkyl-protected groups, the protected polymercan be mixed with Amberlyst® 15 ion exchange resin and heated at anelevated temperature, for example 150° C., until deprotection iscomplete. Tert-alkyl-protected groups can also be removed by reaction ofthe polymer with para-toluenesulfonic acid, trifluoroacetic acid, ortrimethylsilyliodide. Additional methods of deprotection of thetert-alkyl protecting groups can be found in T. W. Greene and P. G. M.Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, NewYork, 1991, page 41.

Tert-butyldimethylsilyl protecting groups can be removed by treatment ofthe polymer with acid, such as hydrochloric acid, acetic acid,para-toluenesulfonic acid, or Dowex® 50W-X8. Alternatively, a source offluoride ions, for instance tetra-n-butylammonium fluoride, potassiumfluoride and 18-crown-6, or pyridine-hydrofluoric acid complex, can beemployed for deprotection of the tert-butyldimethylsilyl protectinggroups. Additional methods of deprotection of thetert-butyldimethylsilyl protecting groups can be found in T. W. Greeneand P. G. M. Wuts, Protective Groups in Organic Synthesis, SecondEdition, Wiley, New York, 1991, pages 80-83.

In addition, protecting groups can be selectively removed from thepolymer, i.e., deprotecting conditions can be selected so as to removeat least one protecting group without removing other dissimilarprotecting groups, by proper selection of deprotecting reagents andconditions.

The following table details representative experimental conditionscapable of selectively removing protecting groups (more labile) whilemaintaining the integrity of other different protecting groups (morestable).

Labile Stable Conditions t-butyldimethylsilyl t-butyl tetrabutylammoniumfluoride t-butyldimethylsilyl t-butyl 1N HCL t-butyldimethylsilyldialkylamino tetrabutylammonium fluoride t-butyldimethylsilyldialkylamino 1N HCL t-butyl dialkylamino Amberlyst ® resin t-amyldialkylamino Amberlyst ® resin trimethylsilyl t-butyl tetrabutylammoniumfluoride trimethylsilyl t-butyl 1N HCL trimethylsilyl dialkylaminotetrabutylammonium fluoride trimethylsilyl dialkylamino 1N HCL

The progress of the deprotection reactions can be monitored byconventional analytical techniques, such as Thin Layer Chromatography(TLC), Nuclear Magnetic Resonance (NMR), or InfraRed (IR) spectroscopy.

Examples of methods to hydrogenate the polymers of this invention aredescribed in U.S. Pat. Nos. 4,970,254, 5,166,277, 5,393,843 and5,496,898, the entire disclosure of each of which is incorporated byreference. The hydrogenation of the polymer is conducted in situ, or ina suitable solvent, such as hexane, cyclohexane or heptane. Thissolution is contacted with hydrogen gas in the presence of a catalyst,such as a nickel catalyst. The hydrogenation is typically performed attemperatures from 25° C. to 150° C., with a archetypal hydrogen pressureof 15 psig to 1000 psig. The progress of this hydrogenation can bemonitored by InfraRed (IR) spectroscopy or Nuclear Magnetic Resonance(NMR) spectroscopy. The hydrogenation reaction is conducted until atleast 90% of the aliphatic unsaturation has been saturated. Thehydrogenated polymer is then recovered by conventional procedures, suchas removal of the catalyst with aqueous acid wash, followed by solventremoval or precipitation of the polymer.

In another aspect of the invention, multi-branched or star-shapedpolymers which include polar monomers are also provided, includingmulti-branched or star-shaped polymers with protected functional groups,their optionally hydrogenated analogues, and the polymers produced byremoval of the protecting groups. The star polymers in this aspect ofthe invention can be produced using the functional initiators (III)described above (singly or combinations thereof), which, by design,incorporate the versatility of functional branch end star polymers. Forexample, hydroxy-, thio-, and/or amino-terminated functional branchescan be copolymerized with comonomers, such as organic diacids (such ascarboxylic acids), diisocyanates, and the like. The copolymers can alsoinclude non-functional branches in the polymer to provide improvedimpact resistance in molecules resulting from further copolymerizationof the star-shaped polymers of the invention with other functionalcomonomers, for example, resultant polyester and/or polyamide molecules.

Novel multi-branched or star-shaped polymers having functional ends canbe produced by polymerizing polar monomers, either singly, sequentially,or as mixtures thereof, with protected functional organolithiuminitiators of Formula (III) above (singly or combinations thereof toprovide arms having different protecting groups and/or differentfunctional groups), and subsequently reacting the resulting polymer withsuitable multifunctional linking agents. This can lead to polymer anionchain lengths of approximately the same size.

Suitable linking or coupling agents include, without limitation,reactive halogen compounds, such as α,α′-dibromo-p-xylene andα,α′,α″-tribromo-mesitylene, multifunctional acrylates, such as ethyleneglycol dimethylacrylate, glycerol trimethacrylate, and the like. Thislinking process is described by J. W. Mays et al. in PolymerInternational, 33 171 (1994). Mixtures of coupling agents may also beused. Generally, the amount of coupling agent used is such that themolar ratio of protected living polymer anions to coupling agent rangesfrom 1:1 to 24:1.

These radiating multi-arm polymers with protected functionality on theends of the arms may be optionally hydrogenated before or after removalof the protecting groups. The star polymers thus formed may havehydroxyl, thio, and/or amino functional branch ends.

Nonfunctional initiators (such as n-butyllithium, sec-butyllithium, andtert-butyllithium) may also be mixed with the functional initiators ofFormula (III) to provide non-functional branch ends as well, which canserve to modify the physical properties of these star-shaped orradiating polymers, especially after their further copolymerization withother functional monomers, such as organic diacids or organicdiisocyanates.

Alternatively, novel multi-branched or star-shaped polymers as inFormula II possessing functional ends (which may be the same ordifferent), and/or both functional and non-functional ends, may beproduced by separately polymerizing polar monomers with protectedfunctional initiators and/or with non-functional organometallicinitiators to separately produce polymer anions, subsequently mixing theresulting separately produced polymer anions, treating the resultingmixture with multifunctional linking agents, and optionallyhydrogenating before or after optionally deprotecting the functionalends of the polymer. This alternative method allows for control of themolecular weight of the arms of the star polymer (for example, differnetpolymer anion chain lengths can be produced) and provides for a moreselective control of the physical properties of the resultant polymers.

If desired, the protecting groups can be removed from the arms of thestar polymer, prior to or after the optional hydrogenation of theresidual unsaturation of the arms, using the techniques described above.This includes selective deprotection when dissimilarly protectedfunctional groups are present, as detailed above.

Molecular weights of the resulting linked or coupled polymers can varydepending on the molecular weight of the polymer anion and the number ofpotential functional linking groups on a coupling agent. The sizes ofthe branches of the linked polymer can be the same or vary.

For example, a protected functional living polymer of this invention canbe generated by reacting 1,1-diphenylethylene with3-(t-butoxy-)propyllithium initiator in THF at −78° C. (Equation 1)followed by polymerization of methyl methacrylate (Equation 2), also inTHF at −78° C.:

Equation 1

(CH₃)₃CO(CH₂)₃Li+(C₆H₅)₂C═CH₂→(CH₃)₃CO(CH₂)₃CH₂C(C₆H₅)₂Li   (V)

The living polymer (VI) may be reacted, for example, with ethylene oxide(Equation 3) to yield a compound of formula (VII), followed byhydrolysis (Equation 4) to produce (VIII),

which may optionally be hydrogenated. Deprotection of polymer (VIII)(Equation 5), for example with dilute para-toluenesulfonic acid, wouldgenerate the dihydroxy polymer (IX)

which contains a functional group on each of the termini of the polymer.

Linking agents, such as those described above, may be used on the activelithium-containing polymer (VI) above to yield polymers, including starpolymers having multiple(s) of the molecular weight of the arms, andfollowing this coupling procedure by the deprotective treatmentdescribed in Equation 5 above, to once again yield telechelicallyfunctional polymers. Thus:

Additionally, a wide variety of symmetrically or asymmetricallyfunctional polymers may be produced by reacting the living polymer (VI)above with various functionalizing agents. For example, addition ofcarbon dioxide (see J. Polym. Sci., Polym. Chem. 30, 2349 (1992)) topolymer (VI) would produce a polymer with one protected hydroxyl and onecarboxyl group, or the living polymer (VI) may be reacted with 1,5diazabicyclo-(3.1.0) hexane as described in U.S. Pat. No. 4,753,991 toproduce a polymer with one protected hydroxyl and one amino group. Apolymer with one protected hydroxyl group and one protected amino groupcan be prepared by reaction of the living anion (VI) with a protectedamino propyl bromide, see Macromolecules, 23, 939 (1990). Reaction ofthe living polymer anion (VI) with oxetane or substituted oxetanes (seeU.S. Pat. No. 5,391,637) would afford a polymer which contained oneprotected hydroxyl and a hydroxyl group. A polymer with two protectedhydroxyl groups can be prepared by reaction of the living anion (VI)with a silicon derived acetal, see U.S. Pat. No. 5,478,899.

Other asymmetrically substituted monofunctional polymers may be producedhaving epoxy or isocyanate groups at one end, for example, by reactingthe lithium salt (VII) above (before hydrolysis), with epichlorohydrinor, by reacting (VIII) itself with an equivalent of a diisocyanate, suchas methylene 4,4-diphenyl diisocyanate (2/1 NCO/OH). Theseunsymmetrically substituted monofunctional polymers could then befurther reacted with other comonomers either with or withoutsimultaneous deprotection as described below.

The protected dihydroxy polymers (VIII) alone and in their hydrogenatedforms could be used as base materials to lend flexibility and higherimpact strength in a number of formulas to produce coatings, sealants,binders and block copolymers with polyesters, polyamides andpolycarbonates as described in UK Patent Application GB2270317A and in“Polytail” data sheets and brochures (Mitsubishi Kasei America).

In the presence of acidic catalysts used to promote the formation ofmany of these block copolymer resins, the protective group of thehydrogenated polymer is removed as well, allowing the exposed hydroxylgrouping in the base polymer molecule to simultaneously participate inthe block copolymer reaction.

For example, hydrogenated polymers (VIII) may be reacted with bisphenolA and phosgene in the presence of appropriate catalysts withsimultaneous deprotection to yield a polycarbonate alternating blockcopolymer. The resulting products are useful as molding resins, forexample, to prepare interior components for automobiles.

A segmented polyamide-hydrogenated block copolymer is also useful as amolding composition to prepare exterior automotive components and can beprepared, for example, by reacting hydrogenated (VIII) polymer withcaprolactam or adipic acid and a diamine in the presence of a suitablecatalyst.

A segmented polyester-hydrogenated block copolymer is produced byreaction of hydrogenated (VIII) polymer with dimethyl terephthalate anda diol along with a suitable acidic catalyst. Again, the products areuseful as molding compounds for exterior automotive components.

Isocyanate-terminated prepolymers can be produced from hydrogenated(VIII) polymers by reaction with suitable diisocyanates (2/1 NCO/OH) asabove and which can be further reacted with diols and additionaldiisocyanates to form segmented polyurethanes useful for water based,low VOC coatings. Inclusion of acid functional diols, such asdimethylolpropionic acid, in the polyurethane introduces pendantcarboxyl groups which can be neutralized with tertiary amines to affordwater dispersable polyolefin/polyurethane segmented polymers, useful forwater based coatings. This same principle could be applied to acrylicpolymers made with tertiary amine functional monomers included, whichcould be made by free radical polymerization following reacting thehydroxyl groups at the terminal ends of the polymer with acryloylchloride or methacryloyl chloride. Segmented polyurethane prepolymersmay be mixed with tackifying resins and used as a moisture-curablesealant, caulk or coating.

Another possible application in coatings would be the use of newdendrimers, based on the use of the polymer with hydroxyl functionalityat the termini thereof to form the core for dendritic hybridmacromolecules based on condensation or addition polymerizations,utilizing the hydroxyl functionality as the initiating site (see, forexample Gitsov and Frechet, American Chemical Society PMSE Preprints,Volume 73, August 1995.

Yet another application includes use as toughening polymers for epoxycomposites, utilizing the polymer core with the hydroxyl groupsconverted to half esters by reaction with anhydrides. These epoxyreactive polymers can then be utilized as reactants with epoxy resinsand amines in composite systems. Reacting the hydroxyl functionalpolymers into unsaturated polyesters provides a new polymer tougheningsystem for polyester molding compounds for automotive and other uses.For a review of the use of linear polymers for toughening of epoxies andpolyesters, see “Rubber-Toughened Plastics”, Edited By C. Keith Riew,ACS Advances in Chemistry Series, #222.

Cathodic electrodepositable coatings may be prepared from epoxyfunctional polymers described above by reacting with epoxy resins in thepresence of excess amine or polyamine, to completely react all the epoxygroups, distilling off excess amine, and neutralizing the resultingepoxy-amine adduct with water soluble organic or inorganic acids to formwater soluble, quarternary ammonium containing polymer salts (see forreference, U.S. Pat. Nos. 3,617,458, 3,619,398, 3,682,814, 3,891,527,3,947,348, and 4,093,594). Alternatively, the above epoxy-amine polymeradducts may be converted to quarternary phosphonium or sulfonium ioncontaining polymers, as described in U.S. Pat. No. 3,935,087.

An acrylate-terminated prepolymer curable by free-radical processes canbe prepared from the hydrogenated (VIII) polymer by reaction with adiisocyanate (2NCO/OH) followed by further reaction with hydroxyethylacrylate in the presence of a basic reagent.

Another likely application for acrylate or methacrylate terminated starpolymers include use as viscosity index (V.I.) improvers. Using carboxylfunctional monomers, such as acrylic acid and methacrylic acid, and/oramine functional monomers such as acrylamide, along with free radicalinitiators in further polymerizations, can result in the formation ofpolymer segments at the periphery of each termini with amine or otherfunctionalities which, in addition to the advantageous properties of thepolymers as V.I. improvers, combines the ability to add functionality tothe polymers for dispersant properties (see, for example, U.S. Pat. Nos.5,496,898, 4,575,530, 4,486,573, 5,290,874, and 5,290,868).

The versatility of the hydroxyl functional polymers of this invention,and the wide range of different segmented polymers (polyethers,polyesters, polyamides, polycarbonates, polyurethanes, etc.) which canbe initiated at the hydroxyl groups, leads to numerous possibleapplications as compatibilizers for polymer blends and alloys. Inaddition to the use of such blends for new applications, much recentinterest is generated in the use of compatibilizers to facilitatepolymer waste recycling.

Alternatively, protecting groups may be removed, either before or afteroptional hydrogenation of the aliphatic unsaturation, then the hydroxyterminated polymer may be reacted with functional comonomers to producenovel copolymers using these and other processes. Thus, for example, ahydroxy terminated polymer may be hydrogenated, and then reacted withethylene oxide in the presence of potassium tert-butoxide to produce apoly(ethyleneoxide)-hydrogenated block copolymer. This reaction sequenceaffords a hydrogel.

Alternatively, the protected monohydroxy terminated polymer (VIII) maybe reacted with functional comonomers, without simultaneously removingthe protective group. These copolymers then may be deprotected and thenfurther reacted with the same or different comonomers to form yet othernovel copolymers. Thus, for example, the hydroxyterminated polymer offormula (VIII) may be hydrogenated, and then reacted with ethylene oxidein the presence of potassium tert-butoxide to produce a poly(ethyleneoxide)-hydrogenated polymethyl methacrylate copolymer with one protectedhydroxyl group on the polymethyl methacrylate segment. This hydroxyl canthen be deprotected and a poly(ethylene oxide) polymer having differentchain lengths grown onto both ends of the polymethyl methacrylatesegment.

In another possible application, the living polymer (V) may be reactedwith an alkenylarylhalosilane, such as styrenyldimethylchlorosilane, toyield the corresponding omega-styrenylterminated macromonomer accordingto the teachings of U.S. Pat. No. 5,278,244, which may then be furtherpolymerized by a variety of techniques to yield “comb” polymers which,on deprotection and hydrogenation yield branched polymers withhydroxyfunctionality on the branch-ends. Such multi-functionality can beutilized to graft a water-soluble polymer such as poly(ethylene oxide)onto a hydrophobic polyolefinic core to produce hydrogels.

In still another possible application, hydrogenated hydroxyterminatedbranches of the polymers may be further reacted with acryloyl chlorideor methacryloyl chloride, and the resultant acrylate ormethacrylate-terminated polymer further polymerized with monomersselected from the group of alkyl acrylates, alkyl methacrylates, anddialkylacrylamides to produce hydrogels. Further, acrylate ormethacrylate-terminated polymers may be polymerized by free-radicalprocesses.

Thus, polymers of the following formulas are also contemplated withinthe scope of this invention:

as presented in the amendment dated Sep. 7, 1999:

X′-FG-(Q)_(d)-R_(n)-Z-J-X

wherein:

FG is a protected or non-protected functional group;

Q is a polar hydrocarbyl group derived by incorporation of a polarmonomer selected from group consisting of esters, amides, and nitritesof acrylic and methacrylic acid, and mixtures thereof;

d is an integer from 10 to 2000;

R is a saturated or unsaturated hydrocarbyl group derived byincorporation of a compound selected from the group consisting ofconjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons,and mixtures thereof;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon group which contains 3-25carbon atoms, optionally containing aryl or substituted aryl groups;

J is oxygen, sulfur, or nitrogen;

X is a polymer segment derived by incorporation of a comonomer reactedwith J; and

X′ is a polymer segment derived by incorporation of a comonomer reactedwith FG,

with the proviso that X′-FG and X-J are not the same,

and heterotelechelic polymers having the formula:

FG-(Q)_(d)-R_(n)-Z-J-[A(R¹R²R³)]_(x)

wherein:

FG is a protected or non-protected functional group;

Q is a polar hydrocarbyl group derived by incorporation of a polarmonomer selected from group consisting of esters, amides, and nitritesof acrylic and methacrylic acid, and mixtures thereof;

d is an integer from 10 to 2000;

R is a saturated or unsaturated hydrocarbyl group derived byincorporation of a compound selected from the group consisting ofconjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons,and mixtures thereof;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon group which contains 3-25carbon atoms, optionally containing aryl or substituted aryl groups; and

J is oxygen, sulfur, or nitrogen;

[A(R¹R²R³)]_(x) is a protecting group, in which A is an element selectedfrom Group IVa of the Periodic Table of Elements;

R¹, R², and R³ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl groups containing lower alkyl,lower alkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, and cycloalkyl and substituted cycloalkyl containing 5 to 12carbon atoms; and

x is dependent on the valence of J and varies from one when J is oxygenor sulfur to two when J is nitrogen,

with the proviso that J-[A(R¹R²R³)]_(x) and FG are not the same.

The above polymer can be further reacted by copolymerizing each of saidgroups J-[A(R¹R²R³)]_(x) and FG with at least one comonomer selectedfrom the group consisting of cyclic ethers, diamines, diisocyanates,polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylicacids, polycarboxylic acids, diols, polyols, anhydrides, and mixturesthereof under conditions sufficient to provide a polymer having theformula:

X′-FG-(Q)_(d)-R_(n)-Z-J-X

wherein:

FG, Q, d, R, n, Z, and J have the meanings ascribed above;

X is a polymer segment derived by incorporation of a comonomer reactedwith J; and

X′ is a polymer segment derived by incorporation of a comonomer reactedwith FG,

with the proviso that X′-FG and X-J are not the same.

The following examples further illustrate the invention.

Preparation of the Initiators

EXAMPLE A Preparation of 3-(t-Butyldimethylsilyloxy)-1-PropyllithiumChain Extended with 2 Moles of Isoprene

A 500 ml, three-necked Morton flask was equipped with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter fitted with a thermocouple, a reflux condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium dispersion was washed free of mineral oil with hexane(2×70 ml), and pentane (1×70 ml), then dried in a stream of argon. Thedry dispersion, 5.20 grams (0.749 mole, 2.80 equivalents) wastransferred to the flask with 260 ml cyclohexane. This suspension wasstirred at 450 RPMs, and heated to 65° C. with a heating mantle. Theheat source was removed. 1-(t-Butyldimethylsilyloxy)-3-chloro-propane,58.82 grams (0.268 mole, 1.00 equivalent) was added dropwise. Anexotherm was detected after 31.8% of the feed had been added. A dryice/hexane cooling bath was applied to maintain the reaction temperatureat 60-65° C. The total feed time was one hundred five minutes. Anexotherm was noted until the last drop of feed was added, then thetemperature fell off rapidly to room temperature. The reaction mixturewas stirred at room temperature for forty five minutes, then heated to65° C. with a heating mantle. The heat source was removed. Isoprene,36.45 grams (0.535 mole, 2.00 equivalents) was then added dropwise. Anexotherm was noted after 24.6% of the feed had been added. Hexanecooling was applied to maintain the reaction temperature at 60-65° C.The total isoprene feed time was thirty eight minutes. The reactionmixture was allowed to stir at room temperature for one hour, thentransferred to a small pressure filter with argon pressure. Very rapidfiltration was observed with 2 psi argon. The muds were reslurried withcyclohexane (2×50 ml). This afforded an orange solution, yield=530 ml,425.34 grams. Total base =17.1 wt. %; Active C—Li=15.9 wt %; Yield(based on active C—Li)=80.8%.

EXAMPLE B Preparation of 3-(t-Butyldimethylsilylthio)-1-propyllithiumChain Extended with 2 Moles of Isoprene

A 500 ml, three-necked Morton flask is equipped with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter fitted with a thermocouple, a reflux condenser, and an argoninlet. This apparatus is dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium dispersion is washed free of mineral oil with hexane(2×70 ml), and pentane (1×70 ml), then dried in a stream of argon. Thedry dispersion, 5.20 grams (0.749 mole, 2.80 equivalents) is transferredto the flask with 260 ml cyclohexane. This suspension is stirred at 450RPMs, and heated to 65° C. with a heating mantle. The heat source isremoved. 1-(t-Butyldimethylsilylthio)-3-chloro-propane, 60.22 grams(0.268 mole, 1.00 equivalent) is added dropwise. An exotherm is detectedafter 21.8% of the feed has been added. A dry ice/hexane cooling bath isapplied to maintain the reaction temperature at 60-65° C. The total feedtime is one hundred minutes. An exotherm is noted until the last drop offeed is added, then the temperature falls off rapidly to roomtemperature. The reaction mixture is stirred at room temperature forforty five minutes, then heated to 65° C. with a heating mantle. Theheat source is removed. Isoprene, 36.45 grams (0.535 mole, 2.00equivalents) is then added dropwise. An exotherm is noted after 24.6% ofthe feed has been added. Hexane cooling is applied to maintain thereaction temperature at 60-65° C. The total isoprene feed time is thirtyeight minutes. The reaction mixture is allowed to stir at roomtemperature for one hour, then transferred to a small pressure filterwith argon pressure. Very rapid filtration is achieved with 2 psi argon.The muds are reslurried with cyclohexane (2×50 ml). This affords anorange solution; yield=530 ml, 435.21 grams. Total base=17.7 wt. %;Active C—Li=16.9 wt %; Yield (based on active C—Li)=82.4%.

EXAMPLE C Preparation of 3-(N,N-Dimethylamino)-1-propyllithium ChainExtended with 2 Moles of Isoprene

A 500 ml, three-necked Morton flask was equipped with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter fitted with a thermocouple, a reflux condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium dispersion was washed free of mineral oil with hexane(2×70 ml), and pentane (1×70 ml), then dried in a stream of argon. Thedry dispersion, 10.57 grams (1.520 moles) was transferred to the flaskwith 250 ml cyclohexane. Coarse sand, 45.3 grams, was added to thereaction mixture. This suspension was stirred at 600-675 RPMs, andheated to 37° C. with a heating mantle. The heat source was removed.1-Chloro-3-(N,N-dimethylamino)propane, 19.64 grams (0.1615 mole)dissolved in 120 ml. Cyclohexane was added dropwise. An exotherm (up to52° C.) was detected after 7% of the feed had been added. A dryice/hexane cooling bath was applied to maintain the reaction temperatureat 41-44° C. The total feed time was thirty-two minutes. An exotherm wasnoted until the last drop of feed was added, then the temperature wasmaintained at 36-40° C. for an additional thirty minutes. The reactionmixture was then transferred to a sintered glass filter while stillwarm. The filtration was complete in three minutes with three psi argonpressure. This afforded a hazy suspension. Yield=400 ml, 298.2 grams.Active C—Li=0.361 M (0.469 m/kg) at 40° C. Yield (based on activeC—Li=87%.

The product crystallized from solution upon standing at roomtemperature. The concentration of the clear supernatant solution wasabout 0.3 M.

A dry 500 ml round bottom flask was fitted with a magnetic stir bar, andan argon inlet. This apparatus was purged with argon, then 154.77 grams(0.0726 mole) of the suspension prepared above was added to the flask.Isoprene, 9.4 grams (0.138 mole, 1.90 equivalents) was then added all atonce. The reaction mixture was then heated to 48-49° C. for fortyminutes. This afforded a slightly hazy golden solution, which waspartially vacuum-stripped on the rotary evaporator to afford the productsolution. Yield=43.32 grams. Active C—Li=1.36 M (1.65 m/kg). Recoveredyield (based on active C—Li)=98.5%.

Examples of the Invention—Preparation of Polymers

EXAMPLE 1 Synthesis of t-Butoxy Functionalized Poly(methyl methacrylate)(PMMA)

A glass reactor was equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor was flame sealed to ahigh vacuum line, and evacuated at 120° C. for 8 hours. A solution ofthe initiator, 3-(1,1-dimethylethoxy)-1-propyllithium chain extendedwith 2 moles of isoprene in toluene (3.51×10⁻⁴ moles) was added to thereactor with a syringe via the inlet tube. The inlet tube was then flamesealed, and the reactor was re-evacuated. The solvent was removed fromthe initiator. The reactor was then cooled to −78° C., andtetrahydrofuran (50 ml.) was added from a break seal ampoule.1,1-Diphenylethylene (4.21×10⁻⁴ moles) (1.2 equivalents), was then addedfrom another break seal ampoule. Immediately, the dark red color,characteristic of the highly delocalized diphenyl alkyl anion, appeared.The crossover reaction, monitored by UV/Vis spectroscopy, was completein 30 minutes. Freshly distilled methyl methacrylate (20 wt. % intetrahydrofuran) was then added with rapid stirring from another breakseal ampoule. The reaction was allowed to proceed for 10 minutes at −78°C., then quenched with a mixture of HCl/methanol added from the lastbreak seal ampoule. The polymer was recovered by precipitation intomethanol, and vacuum dried.

The resultant polymer was characterized by ¹H NMR and SEC analyses, andhad the following properties: M_(n)=9.3×10³ g/mole; M_(w)=10.2×10³g/mole; MWD=1.09.

EXAMPLE 2 Deprotection of tert-Butoxy Group from Poly(methylmethacrylate) (PMMA) with Trimethylsilyl Iodide

A 100 ml, three necked flask is fitted with a magnetic stir bar, anitrogen inlet, and a septum. This apparatus is dried in an ovenovernight at 125° C., assembled hot, and allowed to cool in a stream ofnitrogen. Tert-butoxy-PMMA polymer, prepared in Example 1, (0.5 g) andchloroform (25 ml, distilled) are added to the flask. Trimethylsilyliodide (0.45 ml, three-fold molar excess relative to tert-butoxyprotecting groups) is added via syringe. The reaction is stirred at roomtemperature, and is monitored by TLC analysis for the disappearance ofthe starting material. When all the starting material has been consumedby TLC analysis, the reaction mixture is extracted with aqueous sodiumbicarbonate solution three times to remove excess tert-butyl iodide andtrimethylsilyl iodide. The polymer is precipitated in methanol and thenwashed with excess methanol. The solvent is evaporated under reducedpressure to give hydroxy-terminated polymethylmethacrylate polymer.

Complete deprotection is determined by ¹H NMR analysis (loss oftert-butoxy signal).

EXAMPLE 3 Synthesis of Telechelic t-Butoxy Functionalized Poly(methylmethacrylate) (PMMA)

A glass reactor is equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor is flame sealed to ahigh vacuum line, and evacuated at 120° C. for 8 hours. A solution ofthe initiator, 3-(1,1-dimethylethoxy)-1-propyllithium chain extendedwith 2 moles of isoprene in toluene (3.51×10⁻⁴ moles) is added to thereactor with a syringe via the inlet tube. The inlet tube is then flamesealed, and the reactor is re-evacuated. The solvent is removed from theinitiator. The reactor is then cooled to −78° C., and tetrahydrofuran(50 ml) is added from a break seal ampoule.

1,1-Diphenylethylene (4.21×10⁻⁴ moles) (1.2 equivalents) is then addedfrom another break seal ampoule. Immediately, the dark red color,characteristic of the highly delocalized diphenyl alkyl anion, appears.The crossover reaction, monitored by UV/Vis spectroscopy, is complete in30 minutes. Freshly distilled methyl methacrylate in (20 wt. % intetrahydrofuran) is then added with rapid stirring from another breakseal ampoule. The reaction is allowed to proceed for 10 minutes at −78°C., then excess ethylene oxide (1.4×10⁻³) (4 equivalents) is addedthrough the stopcock. When this reaction is complete, the reaction isquenched with a mixture of HCl/methanol added from the last break sealampoule. The polymer is recovered by precipitation into methanol, andvacuum dried.

The resultant polymer is characterized by ¹H NMR and SEC analyses, andhas the following properties: M_(n)=9.3×10³ g/mole; M_(w)=10.2×10³g/mole; MWD=1.09.

EXAMPLE 4 Deprotection of Telechelic tert-Butoxy Group from Poly(methylmethacrylate) (PMMA) with Trimethylsilyl Iodide

A 100 ml, three necked flask is fitted with a magnetic stir bar, anitrogen inlet, and a septum. This apparatus is dried in an ovenovernight at 125° C., assembled hot, and allowed to cool in a stream ofnitrogen. Tert-butoxy-PMMA polymer, prepared in Example 3, (0.5 g) isplaced and chloroform (25 ml, distilled) are added to the flask.Trimethylsilyl iodide (0.45 ml, three-fold molar excess relative totert-butoxy protecting groups) is added via syringe. The reaction isstirred at room temperature, and is monitored by TLC analysis for thedisappearance of the starting material. When all the starting materialhas been consumed by TLC analysis, the reaction mixture is extractedwith aqueous sodium bicarbonate solution three times to remove excesstert-butyl iodide and trimethylsilyl iodide. The polymer is precipitatedin methanol and then washed with excess methanol. The solvent isevaporated under reduced pressure to give telechelic hydroxy-terminatedpolymethylmethacrylate polymer. Complete deprotection is determined by¹H NMR analysis (loss of tert-butoxy signal).

EXAMPLE 5 Synthesis of t-Butoxy Functionalized Poly(methyl methacrylate)(PMMA) Star

A glass reactor was equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor was charged withlithium chloride, 0.03 grams ([LiCl]:[Li⁺]=2:1) and the flame sealed toa high vacuum line, and evacuated at 120° C. for 8 hours. A solution ofthe initiator, 3-(1,1-dimethylethoxy)-1-propyllithium chain extendedwith 2 moles of isoprene in toluene (3.51×10⁻⁴ moles) was added to thereactor with a syringe via the inlet tube. The inlet tube was then flamesealed, and the reactor was re-evacuated. The solvent was removed fromthe initiator. Tetrahydrofuran (50 ml) was distilled into the reactor.The reactor was then flame sealed from the vacuum line. The reactor wascooled to 0° C., then 1,1-diphenylethylene (4.21×10⁻⁴ moles) (1.2equivalents) diluted with 0.2 ml. of cyclohexane, was added from a breakseal ampoule. Immediately, the dark red color, characteristic of thehighly delocalized diphenyl alkyl anion, appeared. The crossoverreaction, monitored by UV/.Vis spectroscopy, was complete in 30 minutes.The reaction mixture was then cooled to −78° C. Freshly distilled,precooled methyl methacrylate 20 (wt. % in tetrahydrofuran), was thenadded with rapid stirring from another break seal ampoule. The reactionwas allowed to proceed for eight minutes at −78° C. then an aliquot waswithdrawn through the precooled sample port, and quenched with acidicmethanol. The resultant polymer was analyzed by SEC and NMR. Immediatelyafter the sample was withdrawn, precooled ethylene glycol dimethacrylate(8.42×10⁻⁴ moles) (2.4 equivalents) was added over five minutes. Thereaction mixture was stirred for thirty minutes, then quenched with amixture of HCl/methanol added from the last break seal ampoule. Thepolymer was recovered by precipitation into methanol, and vacuum dried.

The resultant base polymer was characterized by ¹H NMR and SEC, and hadthe following properties: M_(n)=8.7×10³ g/mole; MWD=1.05.

The resultant star polymer was characterized by ¹H NMR and SEC, and hadthe following properties: M_(n)=3.17×10⁴ g/mole (based on linear PMMAstandards); MWD=1.36; % Unlinked=17%.

EXAMPLE 6 Synthesis of t-Butoxy Functionalized Poly(methyl methacrylate)(PMMA) Star

A glass reactor was equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor was charged withlithium chloride, 0.03 grams, ([LiCl]:[Li⁺]=2:1) and then flame sealedto a high vacuum line, and evacuated at 120° C. for 8 hours. A solutionof the initiator, 3-(1,1-dimethylethoxy)-1-propyllithium chain extendedwith 2 moles of isoprene in toluene (3.51×10⁻⁴ moles) was added to thereactor with a syringe via the inlet tube. The inlet tube was then flamesealed, and the reactor was re-evacuated. The solvent was removed fromthe initiator. Tetrahydrofuran (50 ml) was distilled into the reactor.The reactor was then flame sealed from the vacuum line. The reactor ascooled to 0° C., then 1,1-diphenylethylene (4.21×10⁻⁴ moles) (1.2equivalents) diluted with 0.2 ml of cyclohexane, was added from a breakseal ampoule. Immediately, the dark red color, characteristic of thehighly delocalized diphenyl alkyl anion, appeared. The crossoverreaction, monitored by UV/Vis spectroscopy, was complete in 30 minutes.The reaction mixture was then cooled to −78° C. Then an aliquot waswithdrawn through the precooled sample port, and quenched with acidicmethanol. The resultant polymer was analyzed by SEC and NMR. Immediatelyafter the sample was withdrawn, precooled ethylene glycol dimethacrylate(1.053×10⁻³ moles) (3.0 equivalents) was added over five minutes. Thereaction mixture was stirred for thirty minutes, then quenched with amixture of HCl/methanol added from the last break seal ampoule. Thepolymer was recovered by precipitation into methanol, and vacuum dried.

The resultant base polymer was characterized by ¹H NMR and SEC analyses,and had the following properties: M_(n)=7.2×10³ g/mole; MWD=1.07.

The resultant star polymer was characterized by ¹H NMR and SEC analyses,and had the following properties: M_(n)=7.24×10⁴ g/mole (based on linearPMMA standards); MWD=1.17; % Unlinked=14%.

EXAMPLE 7 Deprotection of tert-Butoxy Group from Poly(methylmethacrylate) (PMMA) Star with Trimethylsilyl Iodide

A 100 ml, three necked flask was fitted with a magnetic stir bar, anitrogen inlet, and a septum. This apparatus was dried in an ovenovernight at 125° C., assembled hot, and allowed to cool in a stream ofnitrogen. Tert-butoxy-PMMA star polymer, prepared in Example 5, (0.5 g)and chloroform (25 ml, distilled) were added to the flask.Trimethylsilyl iodide (0.45 ml, three-fold molar excess relative totert-butoxy protecting groups) was added via syringe. The reaction wasstirred at room temperature, and was monitored by TLC analysis for thedisappearance of the starting material. When all the starting materialhad been consumed by TLC analysis, the reaction mixture was extractedwith aqueous sodium bicarbonate solution three times to remove excesstert-butyl iodide and trimethylsilyl iodide. The polymer wasprecipitated in methanol and then washed with excess methanol. Thesolvent was evaporated under reduced pressure to give hydroxy-terminatedpolymethylmethacrylate star polymer.

Complete deprotection was determined by ¹H NMR analysis (loss oftert-butoxy signal).

EXAMPLE 8 Deprotection of tert-Butoxy Group from Poly(methylmethacrylate) (PMMA) Star with Amberlyst Resin

A 50 ml, round bottom flask was fitted with a magnetic stir bar, areflux condenser, and a nitrogen inlet. This apparatus was driedovernight at 125° C., assembled hot, and allowed to cool in a stream ofnitrogen. Tert-butoxy-PMMA star polymer, prepared in Example 5, 0.3 g)and t-butylbenzene (10 ml) were added to the flask. Ground AmberlystA-15 resin, 0.3 grams, was added to the flask. The reaction flask wasplaced in a thermostated oil bath at 170° C. The solution was stirred atthis temperature for one hour, then allowed to cool to room temperature.The resin was removed by filtration through a fritted glass filter. Thefilter cake was washed with tetrahydrofuran. The solvent was removed ona rotary evaporator, then dried on the vacuum line. This afforded thehydroxy-terminated poly(methyl methacrylate) star polymer.

Complete deprotection was determined by ¹H NMR analysis (loss oftert-butoxy signal).

EXAMPLE 9 Synthesis of t-Butyldimethylsilyloxy FunctionalizedPoly(methyl methacrylate) (PMMA) Star

A glass reactor was equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor was charged withlithium chloride, 0.03 grams, ([LiCl]:[Li⁺]=2:1) and then flame sealedto a high vacuum line, and evacuated at 120° C. for 8 hours. A solutionof the initiator, 3-(t-butyldimethylsilyloxy)-1-propyllithium incyclohexane (3.51×10⁻⁴ moles) was added to the reactor with a syringevia the inlet tube. The inlet tube was then flame sealed, and thereactor was re-evacuated. The solvent was removed from the initiator.Tetrahydrofuran (50 ml.) was distilled into the reactor. The reactor wasthen flame sealed from the vacuum line. The reactor was cooled to 0° C.,then 1,1-diphenylethylene (4.21×10⁻⁴ moles) (1.2 equivalents) dilutedwith 0.2 ml. of cyclohexane, was added from a break seal ampoule.Immediately, the dark red color, characteristic of the highlydelocalized diphenyl alkyl anion, appeared. The crossover reaction,monitored by UV/Vis spectroscopy, was complete in 30 minutes. Thereaction mixture was then cooled to −78° C. Freshly distilled, precooledmethyl methacrylate (20 wt. % in tetrahydrofuran), was then added withrapid stirring from another break seal ampoule. The reaction was allowedto proceed for eight minutes at −78° C. Then an aliquot was withdrawnthrough the precooled sample port, and quenched with acidic methanol.The resultant polymer was analyzed by SEC and NMR. Immediately after thesample was withdrawn, precooled ethylene glycol dimethacrylate(1.053×10⁻³ moles) (3.0 equivalents) was added over five minutes. Thereaction mixture was stirred for thirty minutes, then quenched with amixture of HCl/methanol added from the last break seal ampoule. Thepolymer was recovered by precipitation into methanol, and vacuum dried.

The resultant base polymer was characterized by ¹H NMR and SEC, and hadthe following properties: M_(n)=7.8×10³ g/mole; MWD=1.09.

The resultant star polymer was characterized by ¹H NMR and SEC, and hadthe following properties: M_(n)=5.21×10⁴ g/mole (based on linear PMMAstandards); MWD=1.16; % Unlinked=37%.

EXAMPLE 10 Deprotection of tert-Butyldimethylsilyloxy Group fromPoly(methyl methacrylate) (PMMA) Star with Fluoride

A 100 ml, three necked flask is fitted with a magnetic stir bar, anitrogen inlet, and a septum. This apparatus is dried in an ovenovernight at 125° C., assembled hot, and allowed to cool in a stream ofnitrogen. Tert-butyldimethysilyloxy-PMMA star polymer, prepared inExample 9, (0.5 g) and tetrahydrofuran (25 ml, distilled) are added tothe flask. Excess tetrabutylammonium fluoride, 1.0 molar intetrahydrofuran (1.0 ml) is added via syringe. the reaction is stirredat room temperature, and is monitored by TLC analysis for thedisappearance of the starting material. When all the starting materialhas been consumed by TLC analysis, the reaction mixture is extractedwith water (3×25 ml.). The organic solvent is removed on the rotaryevaporator. The deprotected hydroxy-terminated poly(methyl methacrylate)star polymer is isolated by precipitation in methanol, washed withmethanol, and vacuum dried.

Complete deprotection is determined by ¹H NMR analysis (loss oftert-butyldimethylsilyl signal).

EXAMPLE 11 Synthesis of Dimethylamino Functionalized Poly(methylmethacrylate) (PMMA) Star

A glass reactor is equipped with four break-seal reagent ampoules, asampling port attached with a Teflon stopcock, an inlet tube fitted aseptum cap, and a magnetic stir bar. This reactor is charged withlithium chloride, 0.03 grams, ([LiCl]:[Li⁺]=2:1) and then flame sealedto a high vacuum line, and evacuated at 120° C. for 8 hours. A solutionof the initiator, 3-(dimethylamino)-1-propyllithium chain extended withtwo moles of isoprene in cyclohexane (3.51×10⁻⁴ moles) is added to thereactor with a syringe via the inlet tube. The inlet tube is then flamesealed, and the reactor is re-evacuated. The solvent is removed from theinitiator. Tetrahydrofuran (50 ml) is distilled into the reactor. Thereactor is then flame sealed from the vacuum line. The reactor is cooledto 0° C., then 1,1-diphenylethylene (4.21×10⁻⁴ moles) (1.2 equivalents)diluted with 0.2 ml. of cyclohexane, is added from a break seal ampoule.Immediately, the dark red color, characteristic of the highlydelocalized diphenyl alkyl anion, appears. The crossover reaction,monitored by UV/VIs spectroscopy, is complete in 30 minutes. Thereaction mixture is then cooled to −78° C. Freshly distilled, precooledmethyl methacrylate (20 wt. % in tetrahydrofuran), is then added withrapid stirring from another break seal ampoule. The reaction is allowedto proceed for eight minutes at −78° C. Then an aliquot is withdrawnthrough the precooled sample port, and quenched with acidic methanol.The resultant polymer is analyzed by SEC and NMR. Immediately after thesample is withdrawn, precooled ethylene glycol dimethacrylate(1.053×10⁻³ moles) (3.0 equivalents) is added over five minutes. Thereaction mixture is stirred for thirty minutes, then quenched with amixture of HCl/methanol added from the last break seal ampoule. Thepolymer is recovered by precipitation into methanol, and vacuum dried.

The resultant base polymer is characterized by ¹H NMR and SEC analyses,and has the following properties: M_(n)=7.8×10³ g/mole; MWD=1.09.

The resultant star polymer is characterized by ¹H NMR and SEC analyses,and has the following properties: M_(n)=5.21×10⁴ g/mole (based on linearPMMA standards); MWD=1.15; % Unlinked=16%.

The foregoing examples are illustrative of the present invention and arenot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

That which is claimed is:
 1. A polymer having the formula:FG-(Q)_(d)-R_(n)-Z-J-[A(R¹R²R³)]_(x)   (I) wherein: FG is H or aprotected or non-protected functional group; Q is a polar hydrocarbylgroup derived by incorporation of a polar monomer selected from groupconsisting of esters, amides, and nitrites of acrylic and methacrylicacid, and mixtures thereof; d is an integer from 10 to 2000; R is asaturated or unsaturated hydrocarbyl group derived by incorporation of acompound selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof; n is an integer from 0 to 5; Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl groups; J is oxygen, sulfur, ornitrogen; [A(R¹R²R³)]_(x) is a protecting group, in which A is anelement selected from Group IVa of the Periodic Table of Elements; R¹,R², and R³ are each independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl groups containing lower alkyl, loweralkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, and cycloalkyl and substituted cycloalkyl containing 5 to 12carbon atoms; and x is dependent on the valence of J and varies from onewhen J is oxygen or sulfur to two when J is nitrogen.
 2. The polymer ofclaim 1, wherein said polar monomer is methyl methacrylate.
 3. Thepolymer of claim 1, wherein FG is selected from the group consisting ofH, hydroxyl, thio, amino, carboxyl, amide, silyl, acrylate, sulfonicacid, isocyanate, and epoxide.
 4. The polymer of claim 1, wherein A iscarbon or silicon.
 5. The polymer of claim 1, wherein at least a portionof aliphatic unsaturation of said polymer has been saturated withhydrogen.
 6. The polymer of claim 5, wherein at least about 90% of thealiphatic unsaturation has been saturated with hydrogen.
 7. A polymerproduced by polymerizing a monomer selected from the group consisting ofesters, amides, and nitrites of acrylic and methacrylic acid, andmixtures thereof, with a protected functional organometallic initiatorof the formula M-R_(n)-Z-J-[A(R¹R²R³)]_(x)   (III) wherein: M is analkali metal; R is a saturated or unsaturated hydrocarbyl group derivedby incorporation of a compound selected from the group consisting ofconjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons,and mixtures thereof; n is an integer from 0 to 5; Z is a branched orstraight chain hydrocarbon group which contains 3-25 carbon atoms,optionally containing aryl or substituted aryl groups; J is oxygen,sulfur, or nitrogen; A is an element selected from Group IVa of thePeriodic Table of Elements; R¹, R², and R³ are independently selectedfrom hydrogen, alkyl, substituted alkyl groups containing lower alkyl,lower alkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkyl, lower alkylthio, and lower dialkylaminogroups, and cycloalkyl and substituted cycloalkyl containing 5 to 12carbon atoms; and x is dependent on the valence of J and varies from onewhen J is oxygen or sulfur to two when J is nitrogen, to form amono-protected, mono-functionalized living polymer, followed byquenching or functionalizing the living polymer with a functionalizinggroup capable of terminating and end-capping said living polymer.
 8. Thepolymer of claim 7, wherein said monomer is methyl methacrylate.
 9. Thepolymer of claim 7, wherein A is carbon or silicon.
 10. The polymer ofclaim 7, wherein at least a portion of aliphatic unsaturation of saidpolymer has been saturated with hydrogen.
 11. The polymer of claim 15,wherein at least about 90% of the aliphatic unsaturation has beensaturated with hydrogen.
 12. The polymer of claim 7, wherein saidfunctionalizing compound is selected from the group consisting ofethylene oxide, propylene oxide, styrene oxide, oxetane, oxygen, sulfur,carbon dioxide, chlorine, bromine, iodine, chlorotrimethylsilane,styrenyldimethyl chlorosilane, 1,3-propane sultone, caprolactam,N-benzylidene trimethylsilylamide, dimethyl formamide, silicon acetals,1,5-diazabicyclo[3.1.0]hexane, allyl bromide, allyl chloride,methacryloyl chloride, 3-(dimethylamino)propyl chloride,N-(benzylidene)trimethylsilylamine, epichlorohydrin, epibromohydrin, andepiiodohydrin.
 13. The polymer of claim 7, wherein said organometallicinitiator is selected from the group consisting ofomega-(tert-alkoxy)-1-alkyllithiums, omega-(tert-alkoxy)-1-alkyllithiumschain extended with conjugated alkadienes, alkenylsubstituted aromatichydrocarbons, and mixtures thereof,omega-(tert-alkylthio)-1-alkyllithiums,omega-(tert-alkylthio)-1-alkyllithiums chain extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums chain-extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, and omega-(bis-tert-alkylsilylamino)-1-alkyllithiums.
 14. Thepolymer of claim 13, wherein said organometallic initiator is selectedfrom the group consisting of 3-(1,1-dimethylethoxy)-1-propyllithium,3-(tert-butyldimethylsilyloxy)-1-propyllithium,3-(1,1-dimethylethylthio)-1-propyllithium,3-(dimethylamino)-1-propyllithium,3-(di-tert-butyldimethylsilylamino)-1-propyllithium,3-(1,1-dimethylethoxy)-1-propyllithium,3-(1,1-dimethylethoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethoxy)-1-butyllithium,5-(1,1-dimethylethoxy)-1-pentyllithium,6-(1,1-dimethylethoxy)-1-hexyllithium,8-(1,1-dimethylethoxy)-1-octyllithium,3-(1,1-dimethylpropoxy)-1-propyllithium,3-(1,1-dimethylpropoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropoxy)-1-butyllithium,5-(1,1-dimethylpropoxy)-1-pentyllithium,6-(1,1-dimethylpropoxy)-1-hexyllithium,8-(1,1-dimethylpropoxy)-1-octyllithium,3-(t-butyldimethylsilyloxy)-1-propyllithium,3-(t-butyldimethylsilyloxy)-2-methyl-1-propyllithium,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilyloxy)-1-butyllithium,5-(t-butyldimethylsilyloxy)-1-pentyllithium,6-(t-butyldimethylsilyloxy)-1-hexyllithium,8-(t-butyldimethylsilyloxy)-1-octyllithium and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyllithium,3-(dimethylamino)-1-propyllithium,3-(dimethylamino)-2-methyl-1-propyllithium,3-(dimethylamino)-2,2-dimethyl-1-propyllithium,4-(dimethylamino)-1-butyllithium, 5-(dimethylamino)-1-pentyllithium,6-(dimethylamino)-1-hexyllithium, 8-(dimethylamino)-1-propyllithium,4-(ethoxy)-1-butyllithium, 4-(propyloxy)-1-butyllithium,4-(1-methylethoxy)-1-butyllithium,3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,4-(triphenylmethoxy)-1-butyllithium,3-[3-(dimethylamino)-1-propyloxy]-1-propyllithium,3-[2-(dimethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyllithium,3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,4-[3-(dimethylamino)-1-propyloxy]-1-butyllithium,6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,3-[2-(methoxy)-1-ethoxy]-1-propyllithium,3-[2-(ethoxy)-1-ethoxy]-1-propyllithium,4-[2-(methoxy)-1-ethoxy]-1-butyllithium,5-[2-(ethoxy)-1-ethoxy]-1-pentyllithium,3-[3-(methylthio)-1-propyloxy]-1-propyllithium,3-[4-(methylthio)-1-butyloxy]-1-propyllithium,3-(methylthiomethoxy)-1-propyllithium,6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,3-[4-(methoxy)-benzyloxy]-1-propyllithium,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyllithium,3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,8-[4-(methoxy)-benzyloxy]-1-octyllithium,4-[4-(methylthio)-benzyloxy]-1-butyllithium,3-[4-(dimethylamino)-benzyloxy]-1-propyllithium,6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,5-(triphenylmethoxy)-1-pentyllithium,6-(triphenylmethoxy)-1-hexyllithium, and8-(triphenylmethoxy)-1-octyllithium,3-(hexamethyleneimino)-1-propyllithium,4-(hexamethyleneimino)-1-butyllithium,5-(hexamethyleneimino)-1-pentyllithium,6-(hexamethyleneimino)-1-hexyllithium,8-(hexamethyleneimino)-1-octyllithium,3-(t-butyldimethylsilylthio)-1-propyllithium,3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilylthio)-1-butyllithium,6-(t-butyldimethylsilylthio)-1-hexyllithium,3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,3-(1,1-dimethylethylthio)-1-propyllithium,3-(1,1-dimethylethylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethylthio)-1-butyllithium,5-(1,1-dimethylethylthio)-1-pentyllithium,6-(1,1-dimethylethylthio)-1-hexyllithium,8-(1,1-dimethylethylthio)-1-octyllithium,3-(1,1-dimethylpropylthio)-1-propyllithium,3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropylthio)-1-butyllithium,5-(1,1-dimethylpropylthio)-1-pentyllithium,6-(1,1-dimethylpropylthio)-1-hexyllithium, and8-(1,1-dimethylpropylthio)-1-octyllithium, chain extended oligomericanalogs thereof chain extended with a hydrocarbyl group derived byincorporation of a compound selected from the group consisting ofalkadienes, alkenyl substituted aromatic hydrocarbons, and mixturesthereof and mixtures thereof.
 15. The polymer of claim 7, wherein saidmonomer is reacted singly, sequentially, or as a mixture thereof.
 16. Amulti-branched or star-shaped polar polymer having at least onefunctional end produced by polymerizing a polar monomer selected fromgroup consisting of esters, amides, and nitriles of acrylic andmethacrylic acid, singly, sequentially, or as a mixture thereof, with aprotected functional organometallic initiator having the formula:M-R_(n)-Z-J-[A(R¹R²R³)]_(x)   (III) wherein: M is an alkali metal; R isa saturated or unsaturated hydrocarbyl group derived by incorporation ofa compound selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof; n is an integer from 0 to 5; Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl groups; J is oxygen, sulfur, ornitrogen; A is an element selected from Group IVa of the Periodic Tableof Elements; R¹, R², and R³ are independently selected from hydrogen,alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, aryl or substituted aryl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbonatoms; and x is dependent on the valence of J and varies from one when Jis oxygen or sulfur to two when J is nitrogen, to form a mono-protected,mono-functionalized living polymer; and coupling said living polymerwith at least one other living polymer with a linking agent.
 17. Thepolymer of claim 16, wherein the linking agent is selected from thegroup consisting of reactive halogen compounds and multifunctionalacrylates.
 18. The polymer of claim 17, wherein said linking agent isselected from the group consisting of α,α′-dibromo-p-xylene,α,α′,α″-tribromo-mesitylene, ethylene glycol dimethylacrylate andglycerol trimethacrylate.
 19. The polymer of claim 16, wherein saidpolar monomer is methyl methacrylate.
 20. The polymer of claim 16,wherein A is carbon or silicon.
 21. The polymer of claim 16, wherein atleast a portion of aliphatic unsaturation of said polymer has beensaturated with hydrogen.
 22. The polymer of claim 21, wherein at leastabout 90% of the aliphatic unsaturation has been saturated withhydrogen.
 23. The polymer of claim 16, wherein said polymer includes atleast one functional end and at least one non-functional end, preparedby polymerizing a polar monomer selected from group consisting ofesters, amides, and nitrites of acrylic and methacrylic acid, singly,sequentially, or as a mixture thereof, with said protected functionalorganometallic initiator of Formula (III) and in addition with at leastone non-functional organometallic initiator.
 24. The polymer of claim16, wherein said polymer includes at least two functional ends havingdifferent functional groups prepared by polymerizing a polar monomerselected from group consisting of esters, amides, and nitrites ofacrylic and methacrylic acid, singly, sequentially, or as a mixturethereof, with protected functional organometallic initiators of Formula(III) in which J is different.
 25. The polymer of claim 16, wherein saidpolymer includes at least two functional ends having differentprotecting groups prepared by polymerizing a polar monomer selected fromgroup consisting of esters, amides, and nitrites of acrylic andmethacrylic acid, singly, sequentially, or as a mixture thereof, withprotected functional organometallic initiators of Formula (III) in which[A(R¹R²R³)]_(x) is different.
 26. A process for preparing polarpolymers, comprising: polymerizing a polar monomer selected from thegroup consisting of esters, amides, and nitrites of acrylic andmethacrylic acid, and mixtures thereof, with a protected functionalorganometallic initiator of the formula M-R_(n)-Z-J-[A(R¹R²R³)]_(x)  (III) wherein: M is an alkali metal; R is a saturated or unsaturatedhydrocarbyl group derived by incorporation of a compound selected fromthe group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is oxygen, sulfur, or nitrogen;[A(R¹R²R³)]_(x) is a protecting group in which: A is an element selectedfrom Group IVa of the Periodic Table of Elements; R¹, R², and R³ areindependently selected from hydrogen, alkyl, substituted alkyl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,aryl or substituted aryl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, and cycloalkyl and substituted cycloalkylcontaining 5 to 12 carbon atoms; and x is dependent on the valence of Jand varies from one when J is oxygen or sulfur to two when J isnitrogen, to form a mono-protected, mono-functionalized living polymer.27. The process of claim 26, further comprising quenching said livingpolymer after said polymerizing step.
 28. The process of claim 26,further comprising functionalizing said living polymer with afunctionalizing compound capable of terminating or end-capping a livingpolymer after said polymerizing step to form a functional group.
 29. Theprocess of claim 26, wherein said polar monomer is methyl methacrylate.30. The process of claim 26, wherein A is carbon or silicon.
 31. Theprocess of claim 26, further comprising saturating at least a portion ofaliphatic unsaturation of said polymer with hydrogen after saidpolymerizing step.
 32. The process of claim 31, wherein said saturatingstep comprises saturating at least about 90% of the aliphaticunsaturation with hydrogen.
 33. The process of claim 31, wherein saidsaturating step comprises saturating at least a portion of aliphaticunsaturation of said polymer with hydrogen prior to deprotecting saidpolymer.
 34. The process of claim 31, further comprising deprotectingsaid polymer prior to said saturating step.
 35. The process of claim 26,further comprising deprotecting said polymer after said polymerizingstep.
 36. The process of claim 28, wherein said functionalizing stepcomprises functionalizing said living polymer with a functionalizingcompound selected from the group consisting of ethylene oxide, propyleneoxide, styrene oxide, oxetane, oxygen, sulfur, carbon dioxide, chlorine,bromine, iodine, chlorotrimethylsilane, styrenyldimethyl chlorosilane,1,3-propane sultone, caprolactam, N-benzylidene trimethylsilylamide,dimethyl formamide, silicon acetals, 1,5-diazabicyclo[3.1.0]hexane,allyl bromide, allyl chloride, methacryloyl chloride,3-(dimethylamino)-propyl chloride, N-(benzylidene)trimethylsilylamine,epichlorohydrin, epibromohydrin, and epiiodohydrin.
 37. The process ofclaim 26, wherein said organometallic initiator is selected from thegroup consisting of omega-(tert-alkoxy)-1-alkyllithiums,omega-(tert-alkoxy)-1-alkyllithiums chain extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, omega-(tert-alkylthio)-1-alkyllithiums,omega-(tert-alkylthio)-1-alkyllithiums chain extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums,omega-(dialkylamino)-1-alkyllithiums chain-extended with conjugatedalkadienes, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof, and omega-(bis-tert-alkylsilylamino)-1-alkyllithiums.
 38. Theprocess of claim 37, wherein said organometallic initiator is selectedfrom the group consisting of 3-(1,1-dimethylethoxy)-1-propyllithium,3-(tert-butyldimethylsilyloxy)-1-propyllithium,3-(1,1-dimethylethylthio)-1-propyllithium,3-(dimethylamino)-1-propyllithium,3-(di-tert-butyldimethylsilylamino)-1-propyllithium,3-(1,1-dimethylethoxy)-1-propyllithium,3-(1,1-dimethylethoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethoxy)-1-butyllithium,5-(1,1-dimethylethoxy)-1-pentyllithium,6-(1,1-dimethylethoxy)-1-hexyllithium,8-(1,1-dimethylethoxy)-1-octyllithium,3-(1,1-dimethylpropoxy)-1-propyllithium,3-(1,1-dimethylpropoxy)-2-methyl-1-propyllithium,3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropoxy)-1-butyllithium,5-(1,1-dimethylpropoxy)-1-pentyllithium,6-(1,1-dimethylpropoxy)-1-hexyllithium,8-(1,1-dimethylpropoxy)-1-octyllithium,3-(t-butyldimethylsilyloxy)-1-propyllithium,3-(t-butyldimethylsilyloxy)-2-methyl-1-propyllithium,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilyloxy)-1-butyllithium,5-(t-butyldimethylsilyloxy)-1-pentyllithium,6-(t-butyldimethylsilyloxy)-1-hexyllithium,8-(t-butyldimethylsilyloxy)-1-octyllithium and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyllithium,3-(dimethylamino)-1-propyllithium,3-(dimethylamino)-2-methyl-1-propyllithium,3-(dimethylamino)-2,2-dimethyl-1-propyllithium,4-(dimethylamino)-1-butyllithium, 5-(dimethylamino)-1-pentyllithium,6-(dimethylamino)-1-hexyllithium, 8-(dimethylamino)-1-propyllithium,4-(ethoxy)-1-butyllithium, 4-(propyloxy)-1-butyllithium,4-(1-methylethoxy)-1-butyllithium,3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,4-(triphenylmethoxy)-1-butyllithium,3-[3-(dimethylamino)-1-propyloxy]-1-propyllithium,3-[2-(dimethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyllithium,3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,4-[3-(dimethylamino)-1-propyloxy]-1-butyllithium,6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,3-[2-(methoxy)-1-ethoxy]-1-propyllithium,3-[2-(ethoxy)-1-ethoxy]-1-propyllithium,4-[2-(methoxy)-1-ethoxy]-1-butyllithium,5-[2-(ethoxy)-1-ethoxy]-1-pentyllithium,3-[3-(methylthio)-1-propyloxy]-1-propyllithium,3-[4-(methylthio)-1-butyloxy]-1-propyllithium,3-(methylthiomethoxy)-1-propyllithium,6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,3-[4-(methoxy)-benzyloxy]-1-propyllithium,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyllithium,3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,8-[4-(methoxy)-benzyloxy]-1-octyllithium,4-[4-(methylthio)-benzyloxy]-1-butyllithium,3-[4-(dimethylamino)-benzyloxy]-1-propyllithium,6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,5-(triphenylmethoxy)-1-pentyllithium,6-(triphenylmethoxy)-1-hexyllithium, and8-(triphenylmethoxy)-1-octyllithium,3-(hexamethyleneimino)-1-propyllithium,4-(hexamethyleneimino)-1-butyllithium,5-(hexamethyleneimino)-1-pentyllithium,6-(hexamethyleneimino)-1-hexyllithium,8-(hexamethyleneimino)-1-octyllithium,3-(t-butyldimethylsilylthio)-1-propyllithium,3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,4-(t-butyldimethylsilylthio)-1-butyllithium,6-(t-butyldimethylsilylthio)-1-hexyllithium,3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,3-(1,1-dimethylethylthio)-1-propyllithium,3-(1,1-dimethylethylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylethylthio)-1-butyllithium,5-(1,1-dimethylethylthio)-1-pentyllithium,6-(1,1-dimethylethylthio)-1-hexyllithium,8-(1,1-dimethylethylthio)-1-octyllithium,3-(1,1-dimethylpropylthio)-1-propyllithium,3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropylthio)-1-butyllithium,5-(1,1-dimethylpropylthio)-1-pentyllithium;6-(1,1-dimethylpropylthio)-1-hexyllithium, and8-(1,1-dimethylpropylthio)-1-octyllithium, chain extended oligomericanalogs thereof chain extended with a hydrocarbyl group derived byincorporation of a compound selected from the group consisting ofalkadienes, alkenyl substituted aromatic hydrocarbons, and mixturesthereof and mixtures thereof.
 39. The process of claim 26, wherein saidpolar monomers are reacted singly, sequentially, or as mixtures thereofwith one another or with other polar comonomers.
 40. The process ofclaim 28, further comprising copolymerizing said functional group withat least one comonomer after said functionalizing step.
 41. The processof claim 40, wherein said comonomer is selected from the groupconsisting of lactams, cyclic ethers, diamines, diisocyanates,polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylicacids, polycarboxylic acids, diols, polyols, anhydrides, and mixturesthereof.
 42. The polymer of claim 1, wherein FG comprises a reactiveolefinic bond capable of polymerizing with a polymerizable monomer. 43.The polymer of claim 7, wherein at least one or both of said functionalgroup comprises a reactive olefinic bond capable of polymerizing with apolymerizable monomer.
 44. The process of claim 28, wherein saidfunctional group comprises a reactive olefinic bond capable ofpolymerizing with a polymerizable monomer.
 45. A polymer having theformula: X′-FG-(Q)_(d)-R_(n)-Z-J-X wherein: FG is a protected ornon-protected functional group; Q is a polar hydrocarbyl group derivedby incorporation of a polar monomer selected from group consisting ofesters, amides, and nitrites of acrylic and methacrylic acid, andmixtures thereof; d is an integer from 10 to 2000; R is a saturated orunsaturated hydrocarbyl group derived by incorporation of a compoundselected from the group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is oxygen, sulfur, or nitrogen; X is apolymer segment derived by incorporation of a comonomer reacted with J;and X′ is a polymer segment derived by incorporation of a comonomerreacted with FG, with the proviso that X′-FG and X-J are not the same.46. The polymer of claim 45, wherein said comonomers are selected fromthe group consisting of cyclic ethers, diamines, diisocyanates,polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylicacids, polycarboxylic acids, diols, polyols, anhydrides and mixturesthereof.
 47. A heterotelechelic polymer having the formula:FG-(Q)_(d)-R_(n)-Z-J-[A(R¹R²R ³)]_(x) wherein: FG is a protected ornon-protected functional group; Q is a polar hydrocarbyl group derivedby incorporation of a polar monomer selected from group consisting ofesters, amides, and nitrites of acrylic and methacrylic acid, andmixtures thereof; d is an integer from 10 to 2000; R is a saturated orunsaturated hydrocarbyl group derived by incorporation of a compoundselected from the group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; and J is oxygen, sulfur, or nitrogen;[A(R¹R²R³)]_(x) is a protecting group, in which A is an element selectedfrom Group IVa of the Periodic Table of Elements; R¹, R², and R³ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, aryl or substituted aryl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbonatoms; and x is dependent on the valence of J and varies from one when Jis oxygen or sulfur to two when J is nitrogen, with the proviso thatJ-[A(R¹R²R³)]_(x) and FG are not the same.
 48. A process for preparing aheterotelechelic polymer, comprising: polymerizing a polar monomerselected from the group consisting of esters, amides, and nitrites ofacrylic and methacrylic acid, and mixtures thereof, with a protectedfunctional organometallic initiator of the formula M-R_(n)-Z-J-[A(R¹R²R³)]_(x) wherein: M is an alkali metal; R is a saturated orunsaturated hydrocarbyl group derived by incorporation of a compoundselected from the group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is oxygen, sulfur, or nitrogen;[A(R¹R²R³)]_(x) is a protecting group in which: A is an element selectedfrom Group IVa of the Periodic Table of Elements; R¹, R², and R³ areindependently selected from hydrogen, alkyl, substituted alkyl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,aryl or substituted aryl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, and cycloalkyl and substituted cycloalkylcontaining 5 to 12 carbon atoms; and x is dependent on the valence of Jand varies from one when J is oxygen or sulfur to two when J isnitrogen, to form a mono-protected, mono-functionalized living polymer;and functionalizing said living polymer with a functionalizing agent toprovide a heterotelechelic polymer having the formula:FG-(Q)_(d)-R_(n)-Z-J-[A(R¹R²R³)]_(x) wherein: FG is a protected ornon-protected functional group; Q is a polar hydrocarbyl group derivedby incorporation of a polar monomer selected from group consisting ofesters, amides, and nitriles of acrylic and methacrylic acid, andmixtures thereof; d is an integer from 10 to 2000; and R, n, Z, J, A,R¹, R², R³, and x have the meanings ascribed above; with the provisothat J-[A(R¹R²R³)]_(x) and FG are not the same.
 49. The process of claim48, further comprising: copolymerizing each of said groupsJ-[A(R¹R²R³)]_(x) and FG with at least one comonomer selected from thegroup consisting of cyclic ethers, diamines, diisocyanates,polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylicacids, polycarboxylic acids, diols, polyols, anhydrides, and mixturesthereof under conditions sufficient to provide a polymer having theformula: X′-FG-(Q)_(d)-R_(n)-Z-J-X wherein: FG, Q, d, R, n, Z, and Jhave the meanings ascribed above; X is a polymer segment derived byincorporation of a comonomer reacted with J; and X′ is a polymer segmentderived by incorporation of a comonomer reacted with FG, with theproviso that X′-FG and X-J are not the same.
 50. A polymer produced bypolymerizing a monomer selected from the group consisting of esters,amides, and nitrites of acrylic and methacrylic acid, and mixturesthereof, in a hydrocarbon solvent, with a protected functionalorganometallic initiator of the formula M-R_(n)-Z-J-[A(R¹R²R³)]_(x)wherein: M is an alkali metal; R is a saturated or unsaturatedhydrocarbyl group derived by incorporation of a compound selected fromthe group consisting of conjugated diene hydrocarbons,alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is aninteger from 0 to 5; Z is a branched or straight chain hydrocarbon groupwhich contains 3-25 carbon atoms, optionally containing aryl orsubstituted aryl groups; J is oxygen, sulfur, or nitrogen;[A(R¹R²R³)]_(x) is a protecting group in which: A is an element selectedfrom Group IVa of the Periodic Table of Elements; R¹, R², and R³ areindependently selected from hydrogen, alkyl, substituted alkyl groupscontaining lower alkyl, lower alkylthio, and lower dialkylamino groups,aryl or substituted aryl groups containing lower alkyl, lower alkylthio,and lower dialkylamino groups, and cycloalkyl and substituted cycloalkylcontaining 5 to 12 carbon atoms; and x is dependent on the valence of Jand varies from one when J is oxygen or sulfur to two when J isnitrogen, to form a mono-protected, mono-functionalized living polymer;quenching or functionalizing the living end of said living polymer; andsubjecting said polymer to conditions sufficient to remove theprotecting group [A(R¹R²R³)]_(x).
 51. The polymer of claim 50, whereinsaid deprotected polymer is further copolymerized with at least onecomonomer.
 52. The polymer of claim 51, wherein said at least onecomonomer is selected from the group consisting of cyclic ethers,diamines, diisocyanates, polyisocyanates, diamides, polyamides, cyclicamides, dicarboxylic acids, polycarboxylic acids, diols, polyols,anhydrides, and mixtures thereof.
 53. A process for preparing polarpolymers, comprising: polymerizing a polar monomer selected from thegroup consisting of esters, amides, and nitrites of acrylic andmethacrylic acid, and mixtures thereof, in a hydrocarbon solvent, with aprotected functional organometallic initiator of the formulaM-R_(n)-Z-J-[A(R¹R²R³)]_(x) wherein: M is an alkali metal; R is asaturated or unsaturated hydrocarbyl group derived by incorporation of acompound selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixturesthereof; n is an integer from 0 to 5; Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl groups; J is oxygen, sulfur, ornitrogen; [A(R¹R²R³)]_(x) is a protecting group in which: A is anelement selected from Group IVa of the Periodic Table of Elements; R¹,R², and R³ are independently selected from hydrogen, alkyl, substitutedalkyl groups containing lower alkyl, lower alkylthio, and lowerdialkylamino groups, aryl or substituted aryl groups containing loweralkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyland substituted cycloalkyl containing 5 to 12 carbon atoms; and x isdependent on the valence of J and varies from one when J is oxygen orsulfur to two when J is nitrogen, to form a mono-protected,mono-functionalized living polymer; and deprotecting said polymer. 54.The process of claim 53, further comprising copolymerizing saiddeprotected polymer with at least one comonomer.
 55. The process ofclaim 54, wherein said at least one comonomer is selected from the groupconsisting of cyclic ethers, diamines, diisocyanates, polyisocyanates,diamides, polyamides, cyclic amides, dicarboxylic acids, polycarboxylicacids, diols, polyols, anhydrides, and mixtures thereof.
 56. Amulti-branched or star-shaped polar polymer having at least onefunctional end produced by polymerizing a polar monomer selected fromgroup consisting of esters, amides, and nitriles of acrylic andmethacrylic acid, singly, sequentially, or as a mixture thereof, in ahydrocarbon solvent, with a protected functional organometallicinitiator having the formula: M-R_(n)-Z-J-[A(R¹R²R³)]_(x) wherein: M isan alkali metal; R is a saturated or unsaturated hydrocarbyl groupderived by incorporation of a compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenylsubstituted aromatichydrocarbons, and mixtures thereof; n is an integer from 0 to 5; Z is abranched or straight chain hydrocarbon group which contains 3-25 carbonatoms, optionally containing aryl or substituted aryl groups; J isoxygen, sulfur, or nitrogen; A is an element selected from Group IVa ofthe Periodic Table of Elements; R¹, R², and R³ are independentlyselected from hydrogen, alkyl, substituted alkyl groups containing loweralkyl, lower alkylthio, and lower dialkylamino groups, aryl orsubstituted aryl groups containing lower alkyl, lower alkylthio, andlower dialkylamino groups, and cycloalkyl and substituted cycloalkylcontaining 5 to 12 carbon atoms; and x is dependent on the valence of Jand varies from one when J is oxygen or sulfur to two when J isnitrogen, to form a mono-protected, mono-functionalized living polymer;coupling said living polymer with at least one other living polymer witha linking agent; and removing at least one [A(R¹R²R³)]_(x) protectinggroup.
 57. The polymer of claim 56, wherein said deprotected polymer iscopolymerized with at least one comonomer.
 58. The polymer of claim 57,wherein said at least one comonomer is selected from the groupconsisting of cyclic ethers, diamines, diisocyanates, polyisocyanates,diamides, polyamides, cyclic amides, dicarboxylic acids, polycarboxylicacids, diols, polyols, anhydrides, and mixtures thereof.
 59. The polymerof claim 42, wherein said reactive olefinic bond is an acrylate ormethacrylate bond.
 60. The polymer of claim 43, wherein said reactiveolefinic bond is an acrylate or methacrylate bond.
 61. The process ofclaim 44, wherein said reactive olefinic bond is an acrylate ormethacrylate bond.